Siloxane polymers and positive working light-sensitive compositions comprising the same

ABSTRACT

A novel siloxane polymer having at least 1 mol % of a structural unit derived from a cyclic heat addition product between a diene compound of formula (I) or (II) and an olefin or acetylene compound of formula (III), (IV) or (V):  (* CHEMICAL STRUCTURE *) (I)  (* CHEMICAL STRUCTURE *) (II)  (* CHEMICAL STRUCTURE *) (III)  (* CHEMICAL STRUCTURE *) (IV)  (* CHEMICAL STRUCTURE *) (V) and a positive working light-sensitive composition comprising the siloxane polymer.

This application is a divisional of application Ser. No. 07/550,446,filed Jul. 10, 1990, now U.S. Pat. No. 5,216,105.

BACKGROUND OF THE INVENTION

The present invention relates to a positive working light-sensitivecomposition which makes it possible to form a presensitized plate foruse in making a lithographic printing plate (hereunder referred to as"PS plate"), proof sheets for process printing, figures for overheadprojectors or fine resist patterns required for making integratedcircuits (IC) of semiconductor elements; components or intermediatesuseful for the preparation of the positive-working light-sensitivecomposition; and a process for the preparation of the components orintermediates.

As so-called positive working light-sensitive materials which are madesoluble by irradiating with actinic rays, for instance, in makinglithographic printing plates, there have been known o-quinonediazidecompounds and these compounds have practically been utilized widely forpreparing PS plates or the like. Such o-quinonediazide compounds aredisclosed in various publications inclusive of U.S. Pat. Nos. 2,766,118;2,767,092; 2,772,972; 2,859,112; 2,907,665; 3,046,110; 3,046,111;3,046,115; 3,046,118; 3,046,119; 3,046,120; 3,046,121; 3,046,122;3,046,123; 3,061,430; 3,102,809; 3,106,465; 3,635,709; and 3,647,443.

These o-quinonediazide compounds are decomposed by irradiation withactinic rays to form 5-membered carboxylic acids and they are thus madealkali-soluble. In these applications of the light-sensitive material,such properties of the compounds are utilised. However, theirlight-sensitivity is insufficient. This problem arises because it isdifficult to optically sensitize the o-quinonediazide compounds andtheir quantum yield essentially never exceeds 1. Moreover, the wavelength used for exposing the same is limited to a specific one and,therefore, tolerance with respect to light sources is narrow. In otherwords, it is difficult to impart resistance to incadescent rays to thecomposition. In addition, the absorption of light in Deep-UV regionranging from about 200 to 300 nm is great and thus it is not suitablefor applications in which light of short wave length is used to enhancethe resolution of a photoresist.

Many attempts have been made to improve the light-sensitivity oflight-sensitive compositions containing o-quinonediazide compounds.However, it is very difficult to improve the light-sensitivity whilemaintaining the development tolerance during development. For instance,examples of such attempts are disclosed in Japanese Patent Publicationfor Opposition Purpose (hereunder referred to as "J.P. KOKOKU") No. Sho48-12242, Japanese Patent Un-examined Publication (hereunder referred toas "J.P. KOKAI") No. Sho 52-40125 and U.S. Pat. No. 4,307,173.

Recently, there have been proposed some positive working light-sensitivecompositions free of o-quinonediazide compounds. One example thereofcomprises a polymeric compound having o-nitrocarbinol ester groups asdisclosed in J.P. KOKOKU No. Sho 56-2696. However, such a compositiondoes not provide high sensitivity for the same reasons as thosediscussed above in connection with o-quinonediazide compounds.

Separately, there have been proposed methods to improvelight-sensitivity using a light-sensitive system which is catalyticallyactivated, wherein a known principle is used that a photolyticallygenerated acid causes a second reaction which makes resist in exposedareas soluble. Examples of the methods include combinations ofphotolytically acid producing compound and acetal or O- or N-acetalcompound (J.P.KOKAI No. Sho 48-89003), orthoester or amideacetalcompound (J.P.KOKAI No. Sho 51-120714), polymer having in the main chainacetal or ketal groups (J.P.KOKAI No. Sho 53-133429), enolether compound(J.P.KOKAI No Sho 55-12995), N-acylimino carbonic acid compound(J.P.KOKAI No. Sho 55-126236), polymer having in the main chainorthoester groups (J.P.KOKAI No. Sho 56-17345), silyl ester compound(J.P.KOKAI No. Sho 60-10247), and silyl ether compound (J.P.KOKAI Nos.Sho 60-37549 and 60-121446). Since quantum yield principally exceeds 1in these combinations, high light-sensitivity is realized. However,there are such problems as storage stability over time, and change insensitivity during the time between exposure to light and development.

There have been also proposed systems which are stable over time at roomtemperature but are decomposed by heat in the presence of an acid tobecome alkali-soluble. Examples of such systems include a combination ofa compound which produces an acid upon exposure to light and secondoryor tertiary carbon (e.g. t-butyl or 2-cyclohexenyl) ester or carbonicacid ester compound disclosed in J.P.KOKAI Nos. Sho 59-45439, 60-3625,62-229242, and 63-36240, Polym. Eng. Sci., vol. 23, page 1012, (1983),ACS. Sym., vol. 242, page 11 (1984). Semiconductor World (1987),November, page 91, Macromolecules, vol. 21, page 1475 (1988) and SPIE,vol. 920, page 42 (1988). In fact, these systems are good in storagestability over time and small in sensitivity change over time afterexposure to light. However, they are low in resistance to oxygen plasmawhen they are used as resist materials for semiconductor.

On the other hand, as pattern-forming methods used in making electronicparts such as semiconductor elements, magnetic bubble memories andintegrated circuits, there have been widely employed methods in which aphotoresist sensitive to ultraviolet and visible rays. The photoresistsare classified into two groups, one of which is negative working typeones whose exposed portions are made insoluble in a developer byirradiating with light, and the other of which is positive working oneswhose exposed portions are, on the contrary, made soluble in adeveloper. The negative working type ones are superior in sensitivity tothe positive working ones and adhesion to a substrate and resistance tochemicals required in wet etching are also excellent. Therefore, the useof negative working resists is one of the mainstreams ofphotolithography. However, the line width and the distance between linesof patterns become smaller as the degree of integration of semiconductorelements and the packaging density thereof are increased. In addition,dry etching techniques have been adopted as a means for etchingsubstrates. Thus, the photoresists should have high resolution and highresistance to dry etching. For this reason, positive workingphotoresists are mainly utilized recently. In particular, there havebeen exclusively used alkali developable positive working photoresistsmainly composed of alkali-soluble novolak resins as disclosed in J. C.Strieter, Kodak Microelectronics Seminar Proceedings, 1976, p. 116,since they are excellent in sensitivity, resolution and resistance todry etching.

However, it is required to further scale down the size of patterns tothus achieve more higher packaging density and degree of integrationaccompanied by the recent increase in multifunctionality and highfunctionality of electronic devices.

More specifically, the size of integrated circuits in their transversaldirection is greatly reduced, but the size thereof in the longitudinaldirection cannot be reduced so much. Therefore, the ratio of the heightof the resist patterns to the width thereof is correspondinglyincreased. For this reason, it becomes very difficult to restrict thechange in size of the resist patterns on a semiconductor wafer having acomplicated stepped structure as the scale down of patterns proceeds. Inaddition, various methods for exposure suffer from problems as the scaledown in the minimum size of patterns. For instance, the exposure bymeans of light causes interference effect due to light reflected by thestepped portions of the substrate which greatly affects dimensionalaccuracy. On the other hand, in the exposure by means of an electronbeam, the ratio of the height to the width of fine resist patternscannot be increased because of the proximity effect caused due tobackscattering of electrons.

It is found that most of these problems can be eliminated by the use ofa multilayered resist system. The multilayered resist system issummarized in Solid State Technology, 74 (1981) and a variety ofinvestigations on the multilayered resist system have been reported. Ingeneral, the multilayered resist methods are classified into triplelayer resist method and double layer resist method. The triple layerresist method comprises applying an organic film for leveling onto thesurface of a stepped substrate, and then applying thereto an inorganicintermediate layer and a resist layer in this order; patterning theresist layer, dry etching the inorganic layer using the patterned resistlayer as a mask, and finally patterning the organic leveling layer by O₂RIE (reactive ion etching) technique using the inorganic layer as a maskto form a desired pattern on the stepped substrate. The investigation ofthis method has been started from earlier stage since it can essentiallyutilize techniques conventionally known, but it requires the use of verycomplicated processes, or since these layers, i.e., an organic film, aninorganic film and an organic film which differ in physical propertiesfrom each other are superposed, the intermediate layer is liable tocause cracks or to form pinholes. Contrary to the triple layer resistmethod, the double layer resist method utilizes a resist havingproperties of both resist and inorganic intermediate layers in thetriple layer resist method, more specifically a resist resistant tooxygen plasma etching and thus the formation of cracks and pinholes canbe suppressed. Further, since the number of layers are reduced from 3 to2, the process can be simplified. However, a conventional resist can beused as the upper resist in the triple layer resist method while, in thedouble layer resist method, it is required to newly develop a resistexcellent in resistance to oxygen plasma.

Under such circumstances, there has been required to develop a highlysensitive positive working photoresist having a high degree ofresolution which is excellent in resistance to oxygen plasma and canhence be used as an upper resist in the double layer resist method orthe like, in particular an alkaline developable resist which can be usedwithout changing the processes currently employed.

As such a resist, there have been proposed light-sensitive compositionscomprising a combination of a conventional o-quinonediazidelight-sensitive material and a silicone polymer such as polysiloxane orpolysilmethylene which is made alkali-soluble, for instance, thosedisclosed in J.P. KOKAI Nos. Sho 61-256347, Sho 61-144639, Sho62-159141, Sho 62-191849, Sho 62-220949, Sho 62-229136, Sho 63-90534 andSho 63-91654 and U.S. Pat. No. 4,722,881.

All these silicone polymers are made alkali soluble by introduction ofphenolic OH group or silanol group (.tbd.Si--OH). The introduction ofphenolic groups are very difficult and silicone polymers having silanolgroups are not always stable over time.

Examples of resists not having orthoquinonediazide compound include alight-sensitive composition comprising a combination of apolysiloxane/carbonate block copolymer and an effective amount of anonium salt disclosed in J.P.KOKAI No. Sho 62-136638, silicone polymerhaving nitrobenzylphenylether groups disclosed in J.P.KOKAI No. Sho63-146038. However, it is very difficult to produce these polymers.Further, alkali solubility of the polymers exposed to light is notsufficient.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide novelpositive working light-sensitive compositions which make it possible tosolve the foregoing problems, more specifically to provide novelpositive working light-sensitive compositions having high sensitivityand high tolerance with respect to light sources.

Another object of the present invention is to provide analkali-developable positive working light-sensitive compositionexhibiting excellent resistance to oxygen plasma.

A further object of the present invention is to provide a novel positiveworking light-sensitive composition which can easily be produced and canhence be easily available.

A still further object of the present invention is to provide novelpositive working light-sensitive compositions which do not produce gasupon exposure to light and do not cause coupling reaction upondevelopment.

A further object of the present invention is to provide a novel siloxanepolymer which can be used as a component or an intermediate of thepositive working light-sensitive composition mentioned above.

A still further object of the present invention is to provide a processfor the preparation of the novel siloxane polymer.

The inventors of this invention have conducted various studies toachieve the foregoing objects and have completed the present invention.

The present invention provides a novel siloxane polymer having at least1 mol % of a structural unit derived from a product of a cyclic heataddition reaction between a diene compound of formula (I) or (II)described below and an olefin or acetylene compound of formula (III),(IV) or (V) described below.

The present invention also provides a novel siloxane polymer having atleast 1 mol % of a structural unit derived from a product of a cyclicheat addition reaction between a diene compound of formula (I) or (II)and an olefin or acetylene compound of formula (V') described below.

The present invention further provides a process for the preparation ofthe siloxane polymer described above.

The present invention further provides a positive workinglight-sensitive composition comprising an alkali soluble polymer and thesiloxane polymer described above.

The present invention further provides a positive workinglight-sensitive composition comprising a compound capable of generatingan acid through irradiation with actinic rays or radiant rays and thesiloxane polymer described above.

The present invention provides a positive working light-sensitivecomposition comprising a condensate of a naphthoquinonediazide compoundand the siloxane polymer described above.

DETAILED EXPLANATION OF THE INVENTION

The present invention, and in particular Formula (I)-(V') discussedabove, will now be explained in detail. ##STR2## wherein R¹ to R⁵ may besame or different and represent hydrogen atoms, alkyl, aryl or alkoxygroups, preferably hydrogen atoms, linear, branched or cyclic alkylgroups having 1 to 10 carbon atoms, mono- or poly-cyclic aryl groupshaving 6 to 15 carbon atoms and alkoxy groups having 1 to 8 carbonatoms;

R⁶ to R⁹ may be same or different and represent hydrogen or halogenatoms, cyano, alkyl, aryl, alkoxy, --SO₂ --R¹², --SO₃ --R¹², --CO--R¹²,--CO--NH--R¹², --COO--R¹², or --Y--A, preferably hydrogen or chlorineatoms, cyano, linear, branched or cyclic alkyl groups having 1 to 6carbon atoms, mono- or poly-cyclic aryl groups having 6 to 10 carbonatoms and alkoxy groups having 1 to 6 carbon atoms, --SO₂ --R¹², --SO₃--R¹², --CO--R¹², --CO--NH--R¹², --COO--R¹², or --Y--A, more preferablyhydrogen atoms, --SO₂ --R¹², --SO₃ --R¹², --CO--R¹², --CO--NH--R¹²,--COO--R¹², or --Y--A;

R¹² represents an alkyl or aryl group, preferably a linear, branched orcyclic alkyl group having 1 to 10 carbon atoms, or a mono- orpoly-cyclic aryl group having 6 to 15 carbon atoms;

R¹⁰ and R¹¹ represent hydrogen atoms, alkyl or aryl groups, preferablyhydrogen atoms or linear or branched alkyl groups having 1 to 4 carbonatoms; two of R⁶ to R⁸ and Y, or R¹⁰ and R¹¹ may combine to form a ring;

Y represents a single bond, a divalent aromatic or aliphatic hydrocarbongroup, preferably a single bond, a linear or branched alkylene grouphaving 1 to 4 carbon atoms, or a mono- or poly-cyclic arylene grouphaving 6 to 10 carbon atoms; Y may contain such a group as ketone,ether, ester, amide, urethane, ureido, etc.;

R²¹⁰ represents an alkyl or aryl group, preferably a linear, branched orcyclic alkyl groups having 1 to 10 carbon atoms or a mono- orpoly-cyclic aryl group having 6 to 15 carbon atoms;

R²¹¹ and R²¹² represent hydrogen atoms, alkyl or aryl groups, preferablyhydrogen atoms or linear or branched alkyl groups having 1 to 4 carbonatoms; R²¹¹ and R²¹² may combine to form a ring; and A represents aphotoreactive or photoresponsible group or an acid decomposable group.

Examples of a photoreactive or photoresponsible group are as follows.##STR3## wherein R²¹³ to R²¹⁵ may be same or different and representalkyl or aryl groups, preferably linear, branched or cyclic alkyl groupshaving 1 to 10 carbon atoms or mono- or poly-cyclic aryl groups having 6to 15 carbon atoms, or aryl groups substituted by an alkyl group having1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, ahalogen atom, a carboxy, carboxyester, cyano, dialkylamino or nitrogroup; B represents a divalent alkylene or arylene group, preferably alinear, branched or cyclic alkylene group having 1 to 12 carbon atoms ora mono- or poly-cyclic arylene group having 6 to 15 carbon atoms; and

Z represents a trivalent alkylene or arylene group, preferably a mono-or poly-cyclic arylene group having 6 to 10 carbon atoms. ##STR4##wherein R³¹³ represents a hydrogen atom, an alkyl or aryl group,preferably a hydrogen atom, a linear, branched or cyclic alkyl grouphaving 1 to 6 carbon atoms;

R³¹⁴ and R³¹⁵ may be same or different and represent hydrogen atoms,nitro, alkoxy or dialkylamino groups, preferably hydrogen atoms or nitrogroups; and

R³¹⁶ represents a hydrogen or halogen atom, a nitrile, alkyl, aryl oralkoxy group, preferably a hydrogen atom, a linear or branched alkylgroup having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbonatoms or a nitrile group. ##STR5## wherein R⁶¹³ represents a hydrogenatom, an alkyl or aryl group, preferably a hydrogen atom, a linear,branched or cyclic alkyl group having 1 to 6 carbon atoms;

R⁶¹⁴ to R⁶¹⁸ may be same or different and represent hydrogen or halogenatoms, alkoxy, aryloxy, cyano or alkyl groups, preferably hydrogen orchlorine atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groupshaving 6 to 15 carbon atoms or linear or branched alkyl groups having 1to 4 carbon atoms, more preferably hydrogen atoms, alkoxy groups having1 to 6 carbon atoms, provided that at least one of R⁶¹⁴ to R⁶¹⁸represents an alkoxy or aryloxy group, preferably at least one of R⁶¹⁴to R⁶¹⁵ represents an alkoxy or aryloxy group, and two of R⁶¹⁴ to R⁶¹⁸may combine to form a ring. Specific examples of A represented by theformula (c) include esters and sulfonates groups of 2-alkoxybenzyl,3-alkoxybenzyl, 2,3-dialkoxybenzyl, 2,4-dialkoxybenzyl,2,5-dialkoxybenzyl, 2,6-dialkoxybenzyl, 3,4-dialkoxybenzyl,3,5-dialkoxybenzyl, 2,3,4-trialkoxybenzyl and 3,4,5,-trialkoxybenzyl.##STR6## wherein R⁷¹² represents an alkyl, alkenyl or aryl group, morespecifically a linear, branched or cyclic alkyl group having preferably1 to 10 carbon atoms, or an alkyl group substituted by a halogen atomsuch as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms suchas a methoxy group, an aryl group such as a phenyl group or an aryloxygroup such as a phenoxy group; an alkenyl group such as a vinyl group ora vinyl group substituted by an alkyl group having 1 to 6 carbon atomssuch as a methyl group, or an aryl group such as a phenyl group; a mono-or di-cyclic aryl group such as a group having 1 to 6 carbon atoms, analkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro, cyano,carboxyl or phenyl group;

R⁷¹³ represents a hydrogen or halogen atom, an alkyl, aryl or alkoxygroup, preferably a chlorine or bromine atom as a halogen atom; an alkylgroup having 1 to 6 carbon atoms, an alkyl group substituted by ahalogen atom such as a chlorine atom or an alkoxy group having 1 to 6carbon atoms; a mono-cyclic aryl group or a mono-cyclic aryl groupsubstituted by an alkyl group having 1 to 6 carbon atoms or by a halogenatom; an alkoxy group having 1 to 6 carbon atoms; and two R⁷¹³ groupsmay combine to form a ring;

R⁷¹⁴ represents an alkyl or aryl group, preferably a linear, branched orcyclic alkyl group having 1 to 10 carbon atoms or a mono- or poly-cyclicaryl group having 6 to 15 carbon atoms or a mono- or poly-cyclic arylgroup having 6 to 15 carbon atoms substituted by an alkyl group having 1to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenatom, a carboxy, carboxyester, cyano, dialkylamino or nitro group;

Ar represents an aryl group, preferably a mono- or di-cyclic aryl groupsuch as a phenyl or naphtyl group or a mono- or di-cyclic aryl groupsubstituted by an alkyl group having 1 to 6 carbon atoms such as amethyl or ethyl group, an alkoxy group having 1 to 6 carbon atoms suchas a methoxy or ethoxy group, a halogen atom such as a chlorine orbromine atom, a nitro, carboxyl, hydroxy, carboxyester, carbonate, cyanoor dialkylamino group; and

n is an integer of 0 to 4.

Examples of acid decomposable groups represented by A are as

Examples of acid decomposable groups represented by A are as follows.

    --CO--O--R.sup.113 or --O--CO--O--R.sup.113                (e)

wherein R¹¹³ represents ##STR7## wherein R¹¹⁴ to R¹¹⁸ may be same ordifferent and represent alkyl or aryl groups, preferably linear orbranched alkyl groups having 1 to 4 carbon atoms or mono- or poly-cyclicaryl groups having 6 to 10 carbon atoms, or linear or branched alkylgroups having 1 to 4 carbon atoms substituted by a halogen atom such asa chlorine or bromine atom; and

R¹¹⁷ to R¹²⁰ may be same or different and represent hydrogen atoms oralkyl groups, preferably linear or branched alkyl groups having 1 to 4carbon atoms. ##STR8## wherein R⁴¹³ to R⁴¹⁸ may be same or different andrepresent alkyl, aryl, aralkyl or --O--R⁴¹⁹ groups, preferably linear,branched or cyclic alkyl groups having 1 to 10 carbon atoms, mono- orpoly-cyclic aryl groups having 6 to 15 carbon atoms or aralkyl groupshaving 7 to 15 carbon atoms, or these groups substituted by a halogenatom, a cyano, nitro or alkoxy group; and

R⁴¹⁹ represents an alkyl or aryl group, preferably a linear, branched orcyclic alkyl group having 1 to 8 carbon atoms or a mono- or poly-cyclicaryl group having 6 to 10 carbon atoms.

A also represent the following group (g). ##STR9## wherein R⁵¹³ and R⁵¹⁴may be same or different and represent hydrogen or halogen atoms, cyano,nitro, alkyl, aryl, alkoxy, --CO--R⁵¹⁵, --COO--R⁵¹⁵, --O--CO--R⁵¹⁵,--NHCO--R⁵¹⁵, --CONH--R⁵¹⁵, --NHCONH--R⁵¹⁵, --NHCOO--R⁵¹⁵ or--OCONH--R⁵¹⁵, preferably hydrogen or chlorine atoms, nitro, linear,branched or cyclic alkyl groups having 1 to 8 carbon atoms, alkoxygroups having 1 to 6 carbon atoms, --CO--R⁵¹⁵, --COO--R⁵¹⁵,--O--CO--R⁵¹⁵, --NHCO--R⁵¹⁵, --CONH--R⁵¹⁵, --NHCONH--R⁵¹⁵, --NHCOO--R⁵¹⁵or --OCONH--R⁵¹⁵, more preferably hydrogen or chlorine atoms, linear orbranched alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1to 4 carbon atoms, --CO--R⁵¹⁵, --COO--R⁵¹⁵, --NHCO--R⁵¹⁵, --CONH--R⁵¹⁵,--NHCONH--R⁵¹⁵ or --OCONH--R⁵¹⁵ ;

R⁵¹⁵ represents an alkyl or aryl group, preferably linear, branched orcyclic alkyl groups having 1 to 10 carbon atoms, or mono- or poly-cyclicaryl groups having 6 to 15 carbon atoms, the aryl groups may besubstituted by an alkyl group having 1 to 6 carbon atoms, an alkoxygroup having 1 to 8 carbon atoms, a halogen atom, a carboxy,carboxyester, cyano or nitro group;

B represents a divalent alkylene or arylene group, preferably a linear,branched or cyclic alkylene group having 1 to 12 carbon atoms or a mono-or poly-cyclic arylene group having 6 to 15 carbon atoms; and arepresents an integer of 1 to 3.

X¹, X² and X³ may be same or different and represent halogen atoms,hydroxy, carboxy, oxime, amide, ureido, amino, alkyl, aryl, aralkyl,alkoxy, aryloxy, --Y--A, ##STR10## preferably chlorine atoms, linear,branched or cyclic alkyl groups having 1 to 10 carbon atoms, mono- orpoly-cyclic aryl groups having 6 to 15 carbon atoms, aralkyl groupshaving 7 to 15 carbon atoms, alkoxy groups having 1 to 8 carbon atoms oraryloxy groups having 6 to 10 carbon atoms, provided that at least twoof X¹, X² and X³ are halogen atoms, hydroxy, carboxy, oxime, amide,ureido, amino, alkoxy or aryloxy groups.

The siloxane polymer of the present invention having a functional groupmay be prepared by a process which comprises the steps of:

(i) subjecting at least one compound of formula (I) or (II) and at leastone compound of formula (III), (Iv) or (v) to a cyclic heat additionreaction;

(ii) hydrolyzing the reaction product of step (i); and

(iii) subjecting the hydrolyzed product of step (ii) to a condensationreaction, whereby a siloxane polymer is produced: or a process whichcomprises the steps of:

(i) hydrolyzing at least one compound of formula (I) or (II);

(ii) subjecting the hydrolyzed product of step (i) to a condensationreaction; and

(iii) subjecting the condensate of step (ii) to a cyclic heat additionreaction with at least one compound of formula (III), (IV) or (V),whereby a siloxane polymer is produced: ##STR11## wherein R¹ to R⁵ maybe same or different and represent hydrogen atoms, alkyl, aryl or alkoxygroups;

R⁶ to R⁹ may be same or different and represent hydrogen or halogenatoms, cyano, alkyl, aryl, alkoxy, --SO₂ --R¹², --SO₃ --R¹², --CO--R¹²,--CO--NH--R¹², --COO--R¹², or --Y--A, wherein R¹² represents an alkyl oraryl group;

R¹⁰ and R¹¹ represent hydrogen atoms, alkyl or aryl groups;

Y represents a single bond, a divalent aromatic or aliphatic hydrocarbongroup;

A represents a functional group;

X¹, X² and X³ may be same or different and represent alkyl, aryl,aralkyl, --Y--A, ##STR12## provided that at least two of X¹, X² and X³are hydrolyzable groups and two of R⁶ to R⁸ and Y or R¹⁰ to R¹¹ maycombine to form a ring.

Specific examples of the functional group include a group having pKa ofnot more than 12, an acid decomposable group and a photoreactive orphotoresponsible group.

In the process of the present invention, at least one compound offormula (XII), (XIII), (XIV), (XV) or (XVI) described later in detailmay coexist and cocondense in the steps of hydrolysis and condensation.

    R.sup.16 --Si--X).sub.3                                    (XII) ##STR13##

Wherein

R¹⁶ to R²², R²⁴ to R²⁶, and R²⁸ to R²⁹ may be same or different and eachrepresents a hydrogen atom or an alkyl, substituted alkyl, aryl,substituted aryl, alkenyl, substituted alkenyl, allyl, silyl,substituted silyl, siloxy or substituted siloxy group,

R²³, R²⁷ and R³⁰ may be same or different and each represents a singlebond, a bivalent alkylene group, a substituted alkylene group, anarylene group or a substituted arylene group, and

X represents a hydrolyzable group.

Further, in the process of the present invention, at least one olefin oracetylene compound of formula (III'), (IV') or (V') may coexist in thestep of cyclic heat addition reaction to be introduced into thestructure of the siloxane polymer: ##STR14## wherein R⁶ to R⁹ may besame or different and represent hydrogen or halogen atoms, cyano, alkyl,aryl, alkoxy, --SO₂ --R¹², --SO₃ --R¹², --CO--R¹², --CO--NH--R¹²,--COO--R¹², or --Y--A, wherein R¹² represents an alkyl or aryl group;

R¹⁰ and R¹¹ represent hydrogen atoms, alkyl or aryl groups;

Y represents a single bond, a divalent aromatic or aliphatic hydrocarbongroup;

A represents a functional group;

B represents a hydrogen atom, an alkyl or aryl group;

provided that two of R⁶ to R⁸ and Y or R¹⁰ to R¹¹ may combine to form aring.

The cyclic heat addition reaction is carried out at a temperatureranging preferably from 50° C. to 200° C., more preferably from 70° C.to 140° C.

Siloxane polymers of the present invention will be explained in detail.

Siloxane Polymer (a)

Siloxane polymer (a) of the present invention containsN-oxyamidesulfonate group ##STR15## or N-oxyimidesulfonate group##STR16## The siloxane polymer per se does not show good alkalisolubility but when irradiated with actinic rays or radiant rays, theN-oxyamidesulfonate or N-oxyimidesulfonate group decomposes to formN-hydroxyamide, N-hydroxyimide or sulfonic acid group which makes thesiloxane polymer alkali soluble.

Siloxane polymer (a) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (a) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene-compound represented by formula (I) or (II) andan olefin or acetylene compound having N-oxyamidesulfonate orN-oxyimidesulfonate group represented by formula (III), (IV) or (V'),that is, so-called Diels-Alder reaction products (VI), (VII), (VIII),(IX), (X') or (XI'). ##STR17## wherein R¹ to R⁹, R²¹⁰ to R²¹², X¹ to X³,Y and A are same as defined above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X') or (XI'), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having N-oxyamidesulfonate orN-oxyimidesulfonate group may coexist with the compound of formula(III), (IV) or (V) so that it is incorporated into the structure of thesiloxane polymer of the present invention.

One or more of compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) may be present in the reaction system and co-condensed to improvethe properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X'), or (XI').

    R.sup.16 --Si--X).sub.3                                    (XII) ##STR18##

In the foregoing formulas, R¹⁶ to R²², R²⁴ to R²⁶, and R²⁸ to R²⁹ may besame or different and each represents a hydrogen atom or an alkyl,substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl,allyl, silyl, substituted silyl, siloxy or substituted siloxy group.

More specifically, the alkyl group may be a linear, branched or cyclicone preferably having about 1 to about 10 carbon atoms and specificexamples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl,decyl, iso-propyl, iso-butyl, tert-butyl, 2-ethylhexyl and cyclohexylgroups. The substituted alkyl group may be those listed above which aresubstituted with a halogen atom such as chlorine atom, an alkoxy grouphaving 1 to 6 carbon atoms such as methoxy group, an aryl group such asphenyl group and/or an aryloxy group such as phenoxy group and specificexamples thereof are monochloromethyl, dichloromethyl, trichloromethyl,bromomethyl, 2-chloroethyl, 2-bromoethyl, 2-methoxyethyl, 2-ethoxyethyl,phenylmethyl, naphthylmethyl and phenoxymethyl groups.

The aryl group may preferably be monocyclic or bicyclic ones such asphenyl, α-naphthyl and β- naphthyl groups. The substituted aryl groupsmay be those listed above which are substituted with alkyl group having1 to 6 carbon atoms such as methyl and ethyl groups; alkoxy groupshaving 1 to 6 carbon atoms such as methoxy and ethoxy groups; halogenatoms such as chlorine atom; and/or nitro, phenyl, carboxy, hydroxy,amido, imido and/or cyano groups. Specific examples thereof are4-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-nitrophenyl,4-hydroxyphenyl, 4-phenylphenyl, 4-methylphenyl, 2-methylphenyl,4-ethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl,2-carboxyphenyl, 4-cyanophenyl, 4-methyl-1-naphtyl, 4-chloro-1-naphthyl,5-nitro-1-naphthyl, 5-hydroxy-1-naphthyl, 6-chloro-2-naphthyl,4-bromo-2-naphthyl and 5-hydroxy-2-naphthyl groups.

The alkenyl group is, for instance, a vinyl group and the substitutedalkenyl group may be a vinyl group which is substituted with alkylgroups such as methyl group and/or aryl groups such as phenyl group.Specific examples of the substituted alkenyl groups are 1-methylvinyl,2-methylvinyl, 1,2-dimethylvinyl, 2-phenylvinyl,2-(p-methylphenyl)vinyl, 2-(p-methoxylphenyl)vinyl, 2-(p-chlorophenyl)vinyl and 2-(o-chlorophenyl)vinyl.

Examples of the silyl, substituted silyl groups are alkyl and/oraryl-substituted silyl groups such as trialkylsilyl and triarylsilylgroups. Such alkyl and aryl groups may be those listed above.

If these substituents each represents a siloxy or substituted siloxygroup, these groups may be those bonded with siloxy or substitutedsiloxy groups of the adjacent structural units or those having atwo-dimensional or three-dimensional structure such as those formed bybonding the siloxy or substituted siloxy group to that of other moleculeas will be described below: ##STR19##

R²³, R²⁷ and R³⁰ may be same or different and each represents a singlebond, a bivalent alkylene group, a substituted alkylene group, anarylene group or a substituted arylene group. More specifically, thealkylene group may be linear, branched or cyclic ones, particularly alinear alkylene group and preferably those having 1 to 10 carbon atomssuch as methylene, ethylene, butylene and octylene groups. Examples ofthe substituted alkylene group are the foregoing alkylene groups whichare substituted with halogen atoms such as chlorine atom, alkoxy groupshaving 1 to 6 carbon atoms and/or aryloxy groups having 6 to 10 carbonatoms.

The arylene group may preferably be monocyclic and bicyclic ones such asphenylene and naphthylene groups. Moreover, examples of the substitutedarylene group are arylene groups which are substituted with alkyl groupshaving 1 to 6 carbon atoms such as methyl and ethyl groups, alkoxygroups having 1 to 6 carbon atoms such as methoxy and ethoxy groupsand/or halogen atoms such as chlorine atom. Specific examples thereofare chlorophenylene, bromophenylene, nitrophenylene, phenylphenylene,methylphenylene, ethylphenylene, methoxyphenylene, ethoxyphenylene,cyanophenylene, methylnaphthylene, chloronaphthylene, bromonaphthyleneand nitronaphthylene groups.

X represents a hydrolyzable group and specific examples thereof includehalogen atoms such as chlorine and bromine atoms; alkoxy groups having 1to 10 carbon atoms such as methoxy, ethoxy and propoxy groups; aryloxygroups having 6 to 10 carbon atoms such as phenoxy group; acyloxy groupshaving 1 to 10 carbon atoms such as acetoxy group; oxime groups having 1to 6 carbon atoms such as methylaldoxime; amido, ureido and aminogroups.

Specific examples of siloxane polymer (a) of the present invention areillustrated below. ##STR20##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (a) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 100% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (b)

Siloxane polymer (b) of the present invention contains nitrobenzyl esteror nitrobenzyl sulfonate group. The siloxane polymer per se does notshow good alkali solubility but when irradiated with actinic rays orradiant rays, the nitrobenzyl ester or nitrobenzyl sulfonate groupdecomposes according to known mechanism to form carboxylic acid orsulfonic acid group which makes the siloxane polymer alkali soluble.

Siloxane polymer (b) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (b) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having nitrobenzyl ester or nitrobenzylsulfonate group represented by formula (III), (IV) or (V), that is,so-called Diels-Alder reaction products (VI), (VII), (VIII), (IX), (X)or (XI). ##STR21## wherein R¹ to R¹¹, X¹ to X³, Y and A are same asdefined above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X) or (XI), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having nitrobenzyl ester ornitrobenzyl sulfonate group may coexist with the compound of formula(III), (IV) or (V) so that it is incorporated into the structure of thesiloxane polymer of the present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Specific examples of siloxane polymer (b) of the present invention areillustrated below. ##STR22##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (b) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 100% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (c)

Siloxane polymer (c) of the Present invention contains alkoxybenzylester or alkoxybenzyl sulfonate group. The siloxane polymer per se doesnot show good alkali solubility but when irradiated with actinic rays orradiant rays, the alkoxybenzyl ester or alkoxybenzyl sulfonate groupdecomposes to form carboxylic acid or sulfonic acid group which makesthe siloxane polymer alkali soluble.

Siloxane polymer (c) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (c) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having alkoxybenzyl ester oralkoxybenzyl sulfonate group represented by formula (III), (IV) or (V),that is, so-called Diels-Alder reaction products (VI), (VII), (VIII),(IX), (X) or (XI) explained above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X) or (XI), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having alkoxybenzyl ester oralkoxybenzyl sulfonate group may coexist with the compound of formula(III), (IV) or (V) so that it is incorporated into the structure of thesiloxane polymer of the present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Specific examples of siloxane polymer (c) of the present invention areillustrated below. ##STR23##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (c) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 100% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (d)

Siloxane polymer (d) of the present invention contains a grouprepresented by --SO₂ --SO₂ --Ar--, ##STR24## The siloxane polymer per sedoes not show good alkali solubility but when irradiated with actinicrays or radiant rays, the group mentioned above decomposes to formsulfinic acid or sulfonic acid group which makes the siloxane polymeralkali soluble.

Siloxane polymer (d) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (d) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having a group of --SO₂ --SO₂ --Ar--,##STR25## represented by formula (III), (IV) or (V), that is, so-calledDiels-Alder reaction products (VI), (VII), (VIII), (IX), (X) or (XI)explained above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X) or (XI), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having a group of --SO₂ --SO₂--Ar--, ##STR26## may coexist with the compound of formula (III), (IV)or (V) so that it is incorporated into the structure of the siloxanepolymer of the present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Specific examples of siloxane polymer (d) of the present invention areillustrated below. ##STR27##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (d) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 100% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (e)

Siloxane polymer (e) of the present invention contains tertiary orsecondary carbon ester or carbonic acid ester group. The siloxanepolymer per se does not show good alkali solubility but when it iscombined with a compound capable of generating an acid throughirradiation of actinic rays or radiant rays, the tertiary or secondarycarbon ester or carbonic acid ester group decomposes to form carboxylicacid, phenol or imide group which makes the siloxane polymer alkalisoluble.

Siloxane polymer (e) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (e) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having tertiary or secondary carbonester or carbonic acid ester group represented by formula (III), (IV) or(V), that is, so-called Diels-Alder reaction products (VI), (VII),(VIII), (IX), (X) or (XI) explained above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X) or (XI), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having tertiary or secondary carbonester or carbonic acid ester group may coexist with the compound offormula (III), (IV) or (V) so that it is incorporated into the structureof the siloxane polymer of the present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Specific examples of siloxane polymer (e) of the present invention areillustrated below. ##STR28##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (e) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 99% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (f)

Siloxane polymer (f) of the present invention contains silyl ether orsilyl ester group. The siloxane polymer per se does not show good alkalisolubility but when it is combined with a compound capable of generatingan acid through irradiation of actinic rays or radiant rays, the silylether or silyl ester group decomposes to form carboxylic acid or phenolgroup which makes the siloxane polymer alkali soluble.

Siloxane polymer (f) of the present invention may be produced by the twosteps: a heat addition reaction between a compound represented byformula (I) or (II) and a compound represented by formula (III), (IV) or(V) and a condensation reaction to form a siloxane skeleton. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (f) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having silyl ether or silyl ester grouprepresented by formula (III), (IV) or (V), that is, so-calledDiels-Alder reaction products (VI), (VII), (VIII), (IX), (X) or (XI)explained above.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more cf the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added, or a method wherein heataddition between the compound of formula (I) or (II) and the compound offormula (III), (IV) or (V) is carried out to form the compound offormula (VI), (VII), (VIII), (IX), (X) or (XI), one or more of whichproduct is hydrolyzed or alkoxylated and then condensed.

An olefin or acetylene compound not having silyl ether or silyl estergroup may coexist with the compound of formula (III), (IV) or (V) sothat it is incorporated into the structure of the siloxane polymer ofthe present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Specific examples of siloxane polymer (f) of the present invention areillustrated below. ##STR29##

In the foregoing examples of the compound, n is an integer of not lessthan 1 and x, y and z each is an integer of not less than 0.

The molecular weight of the siloxane polymer (f) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 99% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Siloxane Polymer (g)

Siloxane polymer (g) of the present invention containsorthoquinonediazide group. The siloxane polymer when irradiated withactinic rays or radiant rays, the orthoquinonediazide group decomposesto form carboxyl group which makes the siloxane polymer alkali soluble.

Siloxane polymer (g) of the present invention may be produced by thethree steps: (i) a heat addition reaction between a compound representedby formula (I) or (II) and a compound represented by formula (III), (IV)or (V), (ii) a condensation reaction to form a siloxane skeleton and(iii) a reaction for introduction of orthoquinonediazide group. In thecourse of the synthesis, it is unnecessary to use a metal catalyst(e.g., sodium, potassium or magnesium compounds) which would have a badeffect to resist properties.

Siloxane polymer (g) of the present invention is a siloxane polymerhaving a structure derived from cyclic heat addition products between asilyl substituted diene compound represented by formula (I) or (II) andan olefin or acetylene compound having phenolic OH, N-hydroxyamide,N-hydroxyimide or anilino group represented by formula (III), (IV) or(V), that is, so-called Diels-Alder reaction products (VI), (VII),(VIII), (IX), (X) or (XI) explained above, to which structureorthoquninonediazide groups have been introduced.

The siloxane polymer of the present invention may be prepared by amethod wherein one or more of the compound of formula (I) or (II) ishydrolyzed or alkoxylated and then condensed, to which the compound offormula (III), (IV) or (V) is heat-added and then 1,2-naphthoquinone-2-diazide-4- or 5-sulfonylhalide is reacted, or amethod wherein heat addition between the compound of formula (I) or (II)and the compound of formula (III), (IV) or (V) is carried out to formthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI), one ormore of which product is hydrolyzed or alkoxylated and then condensed,after which 1, 2-naphthoquinone-2-diazide-4- or 5-sulfonylhalide isreacted.

An olefin or acetylene compound not having phenolic OH, N-hydroxyamide,N-hydroxyimide or anilino group may coexist with the compound of formula(III), (IV) or (V) so that it is incorporated into the structure of thesiloxane polymer of the present invention.

One or more of the compound of formula (XII), (XIII), (XIV), (XV) and/or(XVI) explained earlier may be present in the reaction system andco-condensed to improve the properties of the siloxane polymer.

The siloxane polymer contains at least one mol %, preferably 5 to 95 mol%, more preferably 10 to 80 mol % of the structural unit derived fromthe compound of formula (VI), (VII), (VIII), (IX), (X) or (XI).

Siloxane polymer (g) of the present invention may be prepared byreacting a siloxane polymer having at least one mol % of a structuralunit derived from cyclic heat addition products between a silylsubstituted diene compound represented by formula (I) or (II) and anolefin or acetylene compound represented by formula (III), (IV) or (V),with 1, 2-naphthoquinone-2-diazide-4- or 5-sulfonylhalide in a reactionmedium in the presence of a basic catalyst. An amount of 1,2-naphthoquinone-2-diazide-4- or 5-sulfonylhalide varies depending onthe number of phenolic OH, N-hydroxyamide, N-hydroxyimide or anilinogroup but usually is 0.1 to 1 mol per one equivalent of the group.

The basic catalyst is an amine such as trimethylamine, triethylamine,tripropylamine, pyridine or tetramethylammonium hydroxide, or inorganicalkali such as sodium hydroxide, potassium hydroxide or sodiumcarbonate. An amount of the catalyst used is usually 0.8 to 2.0 mol,preferably 1.0 to 2.0 mol per one mol of 1,2-naphthoquinone-2-diazide-4- or 5-sulfonylhalide.

The reaction medium used in the above reaction is a ketone such asacetone, methyl ethyl ketone or metyl isobutyl ketone, a cyclic ethersuch as dioxane or tetrahydrofuran, a cyclic ketone such ascyclopentanone or cyclohexanone, an amide such as N,N-dimethylformamideor N,N-dimethylacetamide, an ester such as γ-butyrolactone, ethylenecarbonate or propylene carbonate, pyrrolidone, N-methylpyrrolidone orwater. An amount of the reaction medium used is usually 100 to 1000parts by weight per 100 parts by weight of the siloxane polymer. Areaction temperature is usually -30° C. to 60° C., preferably 0° C. to40° C.

Specific examples of siloxane polymer (g) of the present invention areillustrated below. ##STR30##

In the foregoing examples of the compound, D is hydrogen atom or 1,2-naphthoquinone-2-diazide-4- or 5-sulfonyl group. Siloxane polymer (g)of the present invention may contain both hydrogen atom and 1,2-naphthoquinone-2-diazide-4- or 5-sulfonyl group as D but at least 5mol % of D-containing structural units contains 1,2-naphthoquinone-2-diazide-4- or 5-sulfonyl group.

n is an integer of not less than 1 and x, y and z each is an integer ofnot less than 0.

The molecular weight of the siloxane polymer (g) of the invention canfreely be controlled by changing the condensation conditions, butpreferred value thereof is not less than 500, more preferably 1,000 to500,000 expressed in the weight averaged molecular weight.

An amount of the siloxane polymer to be contained in the positiveworking light-sensitive composition is generally 5 to 100% by weight,preferably 20 to 95%, more preferably 30 to 90% by weight based on thesolid content of the light-sensitive composition.

Alkali-soluble Polymers

The positive working light-sensitive composition of the presentinvention may comprise simply the siloxane polymer (a), (b), (c), (d) or(f), but it may further comprise an alkali-soluble polymer.

The alkali-soluble polymers used in the composition are polymerscarrying acidic hydrogen atom having a pKa value of not more than 11such as phenolic hydroxyl group, carboxyl group, sulfonate residue,imido group, sulfonamido group, N-sulfonylamido group,N-sulfonylurethane group and/or active methylene group. Preferredalkali-soluble polymers are novolak type phenol resins such asphenol-formaldehyde resin, o-cresol-formaldehyde resin,m-cresolformaldehyde resin, p-cresol-formaldehyde resin,xylenol-formaldehyde resin and co-condensates thereof. It is alsopossible to simultaneously use the aforesaid phenol resin and acondensate of phenol or cresol substituted with an alkyl group having 3to 8 carbon atoms with formaldehyde such as t-butylphenol/formaldehyderesin as disclosed in J.P. KOKAI No. Sho 50-125806. Examples of otherpolymers usable in the invention are polymers comprising phenolichydroxyl group-containing monomer such as N-(4-hydroxyphenyl)methacrylamide as a copolymerization component; homo- or copolymers ofmonomer(s) such as p-hydroxystyrene, o-hydroxystyrene,m-isopropenylphenol and/or p-isopropenylphenol and partially etherifiedor esterified products thereof.

Further, polymers comprising a carboxyl group-containing monomer such asacrylic acid and methacrylic acid as a copolymerization component;carboxyl group-containing polyvinyl acetal resins as disclosed in J.P.KOKAI No. Sho 61-267042; and carboxyl group-containing polyurethaneresins as disclosed in J.P. KOKAI No Sho 63-124047 can suitably be used.

Polymers comprising repeating units derived from monomers such asN-(4-sulfamoylphenyl) methacrylamide, N-phenylsulfonyl methacrylamideand/or maleimide as copolymerization components: and active methylenegroup-containing polymers as disclosed in J.P. KOKAI No. Sho 63-127237are also used in the composition of the invention.

These alkali-soluble polymers may be used alone or in combination. Anamount of these alkali-soluble polymers to be incorporated into thelight-sensitive composition preferably ranges from 10 to 90% by weight,more preferably 30 to 80% by weight on the basis of the total weight ofthe solid contents of the composition.

Compounds Capable of Generating Acids Through Irradiation of ActinicRays

Examples of suitable compounds which are capable of generating acidsthrough irradiation with actinic rays and which can be used in thepositive working light-sensitive composition of the present invention incombination with siloxane polymer (e) or (f) are various known compoundsand mixtures such as diazonium, phosphonium, sulfonium and iodoniumsalts of BF₄ ⁻⁻, AsF₆ ⁻⁻, PF₆ ⁻⁻, SbF₆ ⁻⁻, SiF₆ ⁻⁻ and ClO₄ ⁻⁻ ; organichalogen compounds: and combinations of organometals and organic halogencompounds. It is also suitably used, in the composition of the presentinvention, compounds capable of generating acids through photolysis asdisclosed in U.S. Pat. No. 3,779,778, German Pat. No. 2,610,842 andEuropean Pat. No. 126,712. addition, compounds which are combined with asuitable dye to give a visible contrast between exposed and unexposedareas when they are exposed to light can also be used in the compositionof the invention. Examples of such compounds are disclosed in, forinstance, J.P. KOKAI Nos. Sho 55-77742 and Sho 57-163234.

Typical examples of the foregoing compounds capable of generating acidsthrough irradiation of actinic rays or radiant rays will hereunder beexplained.

(1) Oxadiazole derivatives or s-triazine derivatives represented byformula (XVII) or (XVIII) which is substituted with a trihalomethylgroup: ##STR31##

In the formulas, R³⁶ represents a substituted or unsubstituted aryl oralkenyl group; R³⁷ represents R³⁶, --CZ₃ or a substituted orunsubstituted alkyl group; and Z represents a halogen atom, inparticular a chlorine or bromine atom.

Specific examples thereof are those listed below: ##STR32##

(2) Iodonium salts or sulfonium salts represented by the followinggeneral formula (XIX) or (XX) respectively: ##STR33##

In these formulas, Ar¹ and Ar² may be same or different and eachrepresents a substituted or unsubstituted aromatic group. Examples ofpreferred substituents of the aromatic groups are alkyl, haloalkyl,cycloalkyl, aryl, alkoxy, nitro, carbonyl, alkoxycarbonyl, hydroxy andmercapto groups and halogen atoms, more preferably alkyl groups having 1to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, nitro groupand chlorine atom. R³⁸, R³⁹ and R⁴⁰ may be same or different and eachrepresents a substituted or unsubstituted alkyl or aromatic group,preferably an aryl group having 6 to 14 carbon atoms, an alkyl grouphaving 1 to 8 carbon atoms or a substituted derivative thereof. Examplesof preferred substituents for the aryl groups are alkoxy groups having 1to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro,carbonyl and hydroxyl groups and halogen atoms and those for alkylgroups are alkoxy groups having 1 to 8 carbon atoms, carbonyl group andalkoxycarbonyl groups. Z¹ ⁻⁻ represents BF₄ ⁻⁻, PF₆ ⁻⁻, AsF₆ ⁻⁻, SbF₆⁻⁻, ClO₄ ⁻⁻, CF₃ SO₃ ⁻⁻. Moreover, two of the groups R³⁸, R³⁹ and R⁴⁰,and Ar¹ and Ar² each may be bonded through a single bond or asubstituent.

Examples of the compounds represented by formula (XIX) are thosedisclosed in J.P. KOKAI Nos. Sho 50-158680 and Sho 51-100716 and J.P.KOKOKU No. Sho 52-14277. Specific examples thereof are as follows:##STR34##

Examples of the compounds represented by formula (XX) are thosedisclosed in J.P. KOKAI No. Sho 51-56885, J.P. KOKOKU No. Sho 52-14278,U.S. Pat. No. 4,442,197 and German Pat. No. 2,904,626. Specific examplesthereof are listed below: ##STR35##

The compounds represented by formulas (XIX) and (XX) are known and canbe prepared, for instance, according to the procedures disclosed in J.W. Knapczyk et al., J. Am. Chem. Soc., 1969, 91, p. 145; A. L. Maycocket al., J. Org. Chem., 1970, 35, p. 2532; E. Goethals et al., Bull. Soc.Chem. Belg., 1964, 73, p. 546; H. M. Leicester, J. Am. Chem. Soc., 1929,51, p. 3587; J. V. Crivello et al., J. Polym. Sci. Polym. Chem. Ed.,1980, 18, p. 2677; U.S. Pat. Nos. 2,807,648 and 4,247,473; F. M.Beringer et al., J. Am Chem. Soc., 1953, 75, p. 2705; and J.P. KOKAI No.Sho 53-101331.

(3) Disulfone derivatives or imidosulfonate derivatives represented byformula (XXI) or (XXII): ##STR36##

In the formulas, Ar³ and Ar⁴ may be same or different and eachrepresents a substituted or unsubstituted aryl group; R⁴¹ represents asubstituted or unsubstituted alkyl or aryl group and B represents asubstituted or unsubstituted alkylene, alkenylene or arylene group.

Specific examples thereof are as follows: ##STR37##

(4) Diazonium salts represented by formula (XXIII):

    Ar.sup.5 --N.sub.2.sup.+ Z.sup.2-                          (XXIII)

wherein Ar⁵ represents a substituted or unsubstituted aromatic group;Z²⁻ represents an organic sulfonate anion, an organic sulfate anion, anorganic carboxylate anion, BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻ or ClO₄ ⁻.

Specific examples thereof are as follows: ##STR38##

An amount of these compounds capable of generating acids to be added tothe composition ranges from 0.001 to 40% by weight, preferably 0.1 to20% by weight, more preferably 1 to 15% by weight based on the totalweight of the solid contents of the composition.

Other Preferred Components

The positive working light-sensitive composition of the presentinvention may optionally comprise other additives such as dyes,pigments, plasticizers and compounds for enhancing photoreactivity orphotoresponsibility and acid-generating efficiency of the foregoingcompounds (so-called sensitizers).

Such sensitizers for enhancing photoreactivity or photoresponsibilityare, for example, benzoin, benzoin metyl ether, 9-fluorenone,2-chloro-9-fluorenone, 2-metyl-9-fluorenone, 9-anthrone,2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-butyl-9,10-anthraquinone,2,6-dichloro-9,10-anthraquinone, xanthone, 2-methyl xanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p-(dimethylamino)phenylstyryl ketone, p-(dimethylamino)phenyl p-methylstyryl ketone,benzophenone, p-(dimethylamino)benzophenone (or Michler's ketone),p-(diethylamino) benzophenone and benzanthrone, most preferablyMichler's ketone.

Other examples of such sensitizers include the compounds of formula(XXIV) disclosed in J.P. KOKOKU No. Sho 51-48516. ##STR39## wherein R⁴²represents an alkyl group (e.g. methyl, ethyl, propyl) or a substitutedalkyl group (e.g. 2-hydroxyethyl, 2-methoxyethyl, carboxymethyl,2-carboxyethyl), R⁴³ represents an alkyl group (e.g. methyl, ethyl) oran aryl group (e.g. phenyl, p-hydroxyphenyl, naphtyl, thienyl), and Drepresents a nonmetallic atom group necessary for forming a heteronucleus containing nitrogen generally used in a cyanine dye, forinstance, benzothiazoles (e.g. benzothiazole, 5-chlorobenzothiazole,6-chlorobenzothiazole), napthothiazoles (e.g. α-naphthothiazole,β-naphthothiazole), benzoselenazoles (e.g. benzoselenazole,5-chlorobenzoselenazole, 6-methoxybenzoselenazole), naphthoselenazoles(e.g. α-naphthoselenazole, β-naphthoselenazole), benzoxazoles (e.g.benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole), naphthoxazoles(e.g. α-naphthoxazole, β-naphthoxazole).

Many specific examples of the compounds of formula (XXIV) are known andcan be selected and used in the present invention.

Preferred examples of such sensitizers include those disclosed in U.S.Pat. No.4,062,686, for example,2-[bis(2-furoyl)methylene]-3-methylbenzothiazoline,2-[bis(2-thienoyl)methylene]-3-methylbenzothiazoline and2-[bis(2-furoyl)methylene]-3-methylnaphtho[1,2-d]thiazoline. Molar ratioof the sensitizer to the structural unit derived from the compound offormula (VI), (VII), (VIII), (IX), (X), (XI), (X') or (XI') is 0.01/1 to5/1, preferably 0.1/1 to 2/1.

Such sensitizers for the acid generator represented by formulas (XIX)and (XX) are, for instance, compounds disclosed in U.S. Pat. Nos.4,250,053 and 4,442,197 Specific examples thereof are anthracene,phenanthrene, perylene, pyrene, chrysene, 1,2-benzanthracene, coronene,1,6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene,2,3,4,5-tetraphenyl furan, 2,5-diphenylthiophene, thioxanthone,2-chlorothioxanthone, phenothiazine, 1,3-diphenyl pyrazoline,1,3-diphenyl isobenzofuran, xanthone, benzophenone,4-hydroxybenzophenone, anthrone, ninhydrin, 9-fluorenone,2,4,7-trinitrofluorenone, indanone, phenanthraquinone, tetralone,7-methoxy-4-methylcoumalin, 3-keto-bis(7-diethylaminocoumalin),Michler's ketone and ethyl Michler's ketone.

Molar ratio of these sensitizers to the compound capable of generatingan acid by photolysis ranges from 0.01/1 to 20/1 and preferably 0.1/1 to5/1.

In addition, dyes may be used as a coloring agent and preferred dyesinclude, for instance, oil-soluble dyes and basic dyes. Specificexamples thereof are Oil Yellow #101, Oil Yellow #130, Oil Pink #312,Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS,Oil Black T-505 (these dyes being available from ORIENT CHEMICALINDUSTRIES, LTD.), Crystal Violet (CI 42555), Methyl Violet (CI 42535),Rhodamine B (CI 45170 B), Malachite Green (CI 42000) and Methylene Blue(CI 52015).

The light-sensitive composition of the present invention may furthercomprise cyclic acid anhydrides, printing out agents for obtaining avisible image immediately after imagewise exposure and other fillers forfurther enhancing the sensitivity thereof. Examples of cyclic acidanhydrides are, as disclosed in U.S. Pat. No. 4,115,128, phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,3,6-endoxy-Δ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalicanhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleicanhydride, succinic anhydride and pyromellitic acid. The sensitivity canbe increased as high as about 3 times at maximum by incorporating thesecyclic acid anhydride into the composition in an amount of 1 to 15% byweight based on the total weight of the composition. Examples ofprinting out agents for obtaining a visible image immediately afterimagewise exposure include a combination of a light-sensitive compoundreleasing an acid upon exposure to light and a salt forming organic dye.Specific examples are a combination ofo-naphthoquinonediazide-4-sulfonyl halide and a salt forming organic dyedisclosed in J.P.KOKAI Nos. Sho 50-36209 and 53-8128 and a combinationof a trihalomethyl compound and a salt forming organic dye disclosed inJ.P.KOKAI Nos. Sho 53-36223 and 54-74728.

Solvent

The positive working light-sensitive composition of the presentinvention is dissolved in a solvent capable of dissolving the componentsof the composition and then applied onto the surface of a substrate ifit is used as a material for PS plates. In addition, if it is used as aresist for processing semiconductors or the like, it is dissolved in asolvent and the solution is used as such. Examples of such solventsherein used are ethylene dichloride, cyclohexanone, methyl ethyl ketone,methanol, ethanol, propanol, ethylene glycol monomethyl ether,1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethylacetate, 2-ethoxyethyl acetate, 1-methoxy-2-propyl acetate,dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide,N,N-dimethylformamide, tetramethyl urea, N-methylpyrrolidone,dimethylsulfoxide, sulforane, γ-butyrolactone, toluene and ethyl acetateand these solvents can be used alone or in combination.

The concentration of the foregoing components (the total solid contentsinclusive of additives) ranges from 2 to 50% by weight. When thesolution is applied onto a substrate, the amount thereof coated variesdepending on the applications and, for instance, as a rule it preferablyranges from 0.5 to 3.0 g/m² based on the solid contents for PS plates.As the amount thereof coated decreases, the light-sensitivitycorrespondingly increases, but, on the contrary, physical properties ofthe resultant film are impaired.

Preparation of PS Plates or the Like

When a PS plate is prepared from the positive working light-sensitivecomposition of this invention, a substrate is in general used andexamples thereof include paper, paper laminated with a plastic film suchas polyethylene, polypropylene or polystyrene film; a metal plate suchas an aluminum (inclusive of aluminum alloys), zinc or copper plate; aplastic film such as a cellulose diacetate, cellulose triacetate,cellulose propionate, cellulose butyrate, cellulose acetate butyrate,cellulose nitrate, polyethylene terephthalate, polyethylene,polystyrene, polypropylene, polycarbonate or polyvinyl acetal film; andpaper or a plastic film listed above which is laminated with a metalfoil or on which a layer or on which a layer of the foregoing metal isdeposited. Particularly preferred is an aluminum plate because of itshigh dimensional stability and low cost. Further, it is also preferredto use a composite sheet comprising a polyethylene terephthalate film onwhich an aluminum sheet is bonded as disclosed in J.P. KOKOKU No. Sho48-18327. The surface of the aluminum plate is preferably grained by,for instance, mechanical methods such as wire brush graining, brushgraining which comprises graining with a nylon brush with pouring aslurry of abrasive particles, ball graining, graining through liquidhoning and buff graining; chemical graining methods such as those inwhich HF, AlCl₃ or HCl is used as an etchant; electrolytic graining inwhich nitric acid or hydrochloric acid is used as an electrolyte; orcombined graining comprising combinations thereof, then optionallyetched with an acid or alkali and anodized in an electrolyte such assulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid,sulfamic acid or a mixture thereof using a DC or AC current to form astrong passivation film on the surface of the aluminum plate. Such apassivation film per se makes the aluminum plate surface hydrophilic,but it is particularly preferred that the aluminum plate is optionallyhydrophilized by subjecting it to a silicate (sodium silicate, potassiumsilicate) treatment as disclosed in U.S. Pat. Nos. 2,714,066 and3,181,461; a potassium fluorozirconate treatment as disclosed in U.S.Pat. No. 2,946,638; a phosphomolybdate treatment as disclosed in U.S.Pat. No. 3,201,247; an alkyl titanate treatment as disclosed in U.K.Pat. No. 1, 108,559; a polyacrylic acid treatment as disclosed in GermanPat. No. 1,091,433; a polyvinyl phosphonic acid treatment as disclosedin German Pat. No. 1,134,093 and U.K. Pat. No. 1,230,447; a phosphonicacid treatment as disclosed in J.P. KOKOKU No Sho 44-6409; a phytic acidtreatment as disclosed in U.S. Pat. No. 3,307,951; a combined treatmentwith a hydrophilic organic polymeric compound and a bivalent metal asdisclosed in J.P. KOKAI Nos. Sho 58-16893 and Sho 58-18291; a treatmentby means of an underlying coating of an water-soluble polymer havingsulfonate groups as disclosed in J.P. KOKAI No. Sho 59-101651. Examplesof other hydrophilization treatments are silicate electrodepositiontreatments as disclosed in U.S. Patent No. 3,658,662.

It is also preferred to use an aluminum plate which is subjected to asealing treatment after graining and anodization treatments. Such asealing treatment can be performed by immersing the aluminum plate inhot water or a hot aqueous solution containing an inorganic or organicsalt or by means of a steam bath.

Actinic Rays or Radiant Rays

Light sources for actinic rays or radiant rays used in the presentinvention are, for instance, a mercury lamp, a metal halide lamp, axenon lamp, a chemical lamp and a carbon arc lamp for actinic rays andelectron rays, X-rays, ion beam and far ultraviolet rays for radiantrays. Preferred examples of light sources are g-rays, i-rays and Deep-UVrays for photoresists. In addition, a scanning exposure technique with ahigh energy density beam such as laser beam or electron rays can beemployed in the invention. Examples of such laser beam sources are aHe·Ne laser, an Ar laser, a Kr ion laser, a He·Cd laser and KrF excimerlaser.

Developer

Examples of developers for the positive working light-sensitivecomposition of the present invention preferably include an aqueoussolution of an inorganic alkali agent such as sodium silicate, potassiumsilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide,tertiary sodium phosphate, secondary sodium phosphate, tertiary ammoniumphosphate, secondary ammonium phosphate, sodium metasilicate, sodiumbicarbonate or ammonia or an organic alkali agent such as tetraalkylammonium hydroxide. These alkaline agents may be used alone or incombination. The concentration thereof ranges from 0.1 to 10% by weightand preferably 0.5 to 5% by weight.

These aqueous alkali solutions may optionally comprise a surfactant oran organic solvent such as an alcohol.

The present invention will hereunder be explained in more detail withreference to the following non-limitative working Examples and theeffects practically achieved by the present invention will also bediscussed in detail.

PREPARATION EXAMPLE 1 Preparation of N-Hydroxyphthalimide ##STR40##

To a solution of 42 g (1.05 mole) of sodium hydroxide in 500 ml ofwater, there was added 73.0 g (1.05 mole) of hydroxylaminehydrochloride. Subsequently, 148 g (1.0 mole) of phthalic anhydride wasadded to the solution and the resulting mixture was stirred at 90° C.for one hour. A solution of 30 g of sulfuric acid in 100 ml of water wasadded to the reaction mixture from which pale yellow solids had beenprecipitated out and the mixture was stirred for additional 30 minutes.The pale yellow solids were filtered off and recrystallized from abenzene/ethanol mixed solvent to give 132 g of the title compound:N-hydroxyphthalimide.

PREPARATION EXAMPLE 2 Preparation of N-Hydroxymaleimide ##STR41##

In the Preparation Example 1, 98 g of maleic anhydride was substitutedfor phthalic anhydride, the resulting mixture was likewise stirred at90° C. for one hour and then 70° C. for 3 hours. The reaction mixturewas allowed to stand at room temperature and the pale brown crystalswere filtered off to give 75 g of the title compound:N-hydroxymaleimide.

PREPARATION EXAMPLE 3 Preparation of N-Benzoyl-N-methylhydroxylamine##STR42##

10.0 g of N-methylhydroxylamine hydrochloride was added to 100 ml oftetrahydrofuran and 19.8 g of pyridine was added to the mixture. To theresulting mixture, there was dropwise added a solution of 16.8 g ofbenzoyl chloride in 100 ml of tetrahydrofuran at room temperature overone hour with stirring. The stirring was continued for additional 8hours to proceed the reaction. After addition of 50 ml of dilutehydrochloric acid, the tetrahydrofuran was removed in vacuo and theremaining solution was extracted with ethyl acetate. The resultantextract was dried over anhydrous magnesium sulfate and then the ethylacetate was removed under reduced pressure. The crude product obtainedwas purified by column chromatography (packed material: silica gel;eluent: ethyl acetate/hexane) to give 8.5 g ofN-benzoyl-N-methylhydroxylamine as an oil having a melting point of notmore than 20° C.

PREPARATION EXAMPLE 4 Preparation of N-hydroxyphthalimido-vinylsulfonate ##STR43##

To a mixture of 3.3 g of N-hydroxyphthalimide and 2.6 g of vinylsulfonylchloride, there was added 50 ml of acetone. 2.0 g of triethylamine wasdropwise added to the mixture over 10 minutes at room temperature (about20° C.) with stirring, then the mixture was stirred at room temperaturefor additional one hour, poured into 200 g of ice-water and theresulting precipitates were recrystallized from a benzene/ethanol mixedsolvent to thus obtain 4.0 g of N-hydroxyphthalimido-vinyl sulfonate.

PREPARATION EXAMPLE 5 Preparation ofN-hydroxymaleimido-1-(4-ethoxynaphthalene)sulfonate ##STR44##

120 ml of acetone was added to a mixture of 5.7 g of N-hydroxymaleimideand 13.5 g of 1-(4-ethoxy-naphthalene)sulfonyl chloride and then thesame procedures used in Preparation Example 4 were repeated to obtain12.4 g of N-hydroxymaleimido-1-(4-ethoxynaphthalene)sulfonate.

PREPARATION EXAMPLE 6 Preparation ofo-vinylsulfonyl-N-benzoyl-N-methylhydroxylamine ##STR45##

130 ml of tetrahydrofuran was added to a mixture of 7.6 g ofN-benzoyl-N-methylhydroxylamine and 6.3 g of vinylsulfonyl chloride anda solution of 5.1 g of triethylamine in 20 ml of tetrahydrofuran wasdropwise added to the mixture over 2 hours with stirring while coolingthe mixture so that the temperature was maintained at 25° C. or less.The reaction was continued for additional 2 hours at a temperatureranging from 15° to 25° C. and then the same procedures used inPreparation Example 4 were repeated to give 9.2 g ofo-vinylsulfonyl-N-benzoyl-N-methylhydroxylamine.

PREPARATION EXAMPLE 7 Preparation of Exemplified Compound (a)-(30)

8.7 g (0.05 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 12.7 g (0.05mole) of N-hydroxyphthalimido-vinylsulfonate were dissolved in 100 ml ofdioxane and stirred at 100° C. for one hour under heating. After coolingto room temperature, 9.9 g (0.05 mole) of trimethoxyphenyl silane wasadded to the mixture. Further, 10 ml of distilled water and 0.1 g ofconcentrated hydrochloric acid were added thereto and the mixture wasstirred for 30 minutes. Then the mixture was heated to remove thesolvent (dioxane) and to thus concentrate the mixture. The resultingconcentrate was added to 1 l of water with stirring and the solidprecipitated out was filtered off and dried in vacuo. Thus, 24 g of abrownish white resin was obtained. It was confirmed that the resin wasexemplified compound (a)-(30) in terms of NMR spectroscopy. In addition,the molecular weight thereof was determined by gel permeationchromatography (GPC) and the weight average molecular weight thereof(polystyrene standard) was found to be 3,500.

PREPARATION EXAMPLE 8 Preparation of Exemplified Compound (a)-(38)

8.7 g of 2-(trimethoxysilyl)-1,3-butadiene and 17.4 g ofN-hydroxymaleimido-1-(4-ethoxy-naphthalene)sulfonate were dissolved in100 ml of dioxane and stirred at 100° C. for one hour under heatingThereafter, 9.9 g of trimethoxyphenyl silane was added to the mixture atroom temperature and then the same procedures used in PreparationExample 7 were repeated to perform the reaction and the post-treatments.Thus, 28 g of a brownish white resin was obtained. The weight averagemolecular weight thereof (GPC; polystyrene standard) was found to be4,200.

EXAMPLES 1 to 6

A 2S aluminum plate having a thickness of 0.24 mm was immersed in 10%aqueous solution of tertiary sodium phosphate maintained at 80° C. for 3minutes to degrease the same, grained with a nylon brush, etched with asodium aluminate solution for about 10 minutes and then desmutted with a3% aqueous solution of sodium hydrogen sulfate. The aluminum plate wasthen anodized at a Current density of 2 A/dm² for 2 minutes in a 20%sulfuric acid solution to thus obtain an aluminum substrate.

Six kinds of solutions, (A)-1 to (A)-6, of light-sensitive composition(hereunder referred to as "light-sensitive solutions") were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (A) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (A)-1 to (A)-6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solutions (A)-1 to(A)-6 are listed in Table I given below.

    ______________________________________                                        Light-sensitive Solution (A)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.50                                                  Cresol/formaldehyde/novolak resin                                                                     1.0                                                   (m/p-cresol ratio = 6/4)                                                      Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Methyl cellosolve       15                                                    ______________________________________                                    

A gray scale having a density difference of 0.15 was brought in closecontact with the light-sensitive layer of each PS plate (A)-1 to (A)-6and the layer was exposed to light from a 2 KW high pressure mercurylamp at a distance of 50 cm for 2 minutes. The exposed PS plates (A)-1to (A)-6 were immersed in and developed with DP-4 (trade name; availablefrom Fuji Photo Film Co., Ltd.) diluted 8 times with water for 60seconds at 25° C. to thus obtain positive images dyed clear blue.

Each of the organopolysiloxane compounds of the present invention usedhad a weight average molecular weight (GPC; polystyrene standard)ranging from 2,000 to 8,000.

Moreover, among the siloxane polymers used, exemplified compounds(a)-(30), (a)-(35), (a)-(38) and (a)-(43), the content of theN-oxyamidosulfonate group- or N-oxyimidosulfonate group-containingsiloxane unit was 50 mole % in each compounds listed above.

                  TABLE I                                                         ______________________________________                                        Ex. No. PS plate siloxane polymer of the invention used                       ______________________________________                                        1       (A)-1    Exemplified Compound (a)-(16)                                2       (A)-2    Exemplified Compound (a)-(20)                                3       (A)-3    Exemplified Compound (a)-(30)                                4       (A)-4    Exemplified Compound (a)-(35)                                5       (A)-5    Exemplified Compound (a)-(38)                                6       (A)-6    Exemplified Compound (a)-(43)                                ______________________________________                                    

EXAMPLES 7 TO 12

The same procedures used in Examples 1 to 6 were repeated to form PSplates (B)-1 to (B)-6 except that the following light-sensitivesolutions (B)-1 to (B)-6 were used. These solutions were prepared byadding 0.05 g each of ethyl Michler's ketone(4,4'-bis(diethylamino)-benzophenone) to the light-sensitive solutions(A)-1 to (A)-6 used in Examples 1 to 6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

    ______________________________________                                        Light-sensitive Solution (B)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.50                                                  Cresol/formaldehyde/novolak resin                                                                     1.1                                                   (m/p-cresol ratio = 6/4)                                                      Ethyl Michler's ketone  0.05                                                  Oil Blue #603 (available from ORIENT                                                                  0.01                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Methyl cellosolve       15                                                    ______________________________________                                    

The resultant PS plates (B)-1 to (B)-6 were exposed to light anddeveloped in the same manner used in Examples 1 to 6. Thus, positiveimages dyed clear blue were obtained in all the cases. The relativeratio of the sensitibity of the PS plate (A)-1 to (A)-6 to that of thePS plate (B)-1 to (B)-6 was calculated from the step number of the grayscales which were clear. The results obtained are listed in thefollowing Table II.

                  TABLE II                                                        ______________________________________                                                                          Relative                                    Ex.           siloxane polymer of the                                                                           Sensitivity                                 No.  PS plate invention used      ratio (B)/(A)                               ______________________________________                                         7   (A)-1    Exemplified Compound (a)-(16)                                                                     3.0                                              (B)-1                                                                     8   (A)-2    Exemplified Compound (a)-(20)                                                                     1.5                                              (B)-2                                                                     9   (A)-3    Exemplified Compound (a)-(30)                                                                     2.5                                              (B)-3                                                                    10   (A)-4    Exemplified Compound (a)-(35)                                                                     3.5                                              (B)-4                                                                    11   (A)-5    Exemplified Compound (a)-(38)                                                                     3.0                                              (B)-5                                                                    12   (A)-6    Exemplified Compound (a)-(43)                                                                     2.0                                              (B)-6                                                                    ______________________________________                                    

As seen from Table II, the addition of Michler's ketone to thelight-sensitive layer leads to the increase in the sensitivity in allthe cases examined.

EXAMPLES 13 TO 18

A comparative PS plate (C) was prepared in the same manner used inExamples 1 to 6 except that a light-sensitive solution (C) was used. Thelight-sensitive solution (C) was prepared by using 0.40 g of1,2-naphthoquinonediazido-5-sulfonate of m-cresol/formaldehyde/novolakresin in place of the siloxane polymer of the invention employed in thelight-sensitive solution (A). The coated amount of the light-sensitivesolution was 1.5 g/m² (weighed after drying).

The PS plates (A)-1 to (A)-6 and the PS plate (C) were allowed to standunder irradiation with light rays from a white fluorescent tube for 10minutes. These PS plates were exposed to light and developed in the samemanner used in Examples 1 to 6 and the change in the sensitivity thereofobserved before and after irradiation with the light rays from the whitefluorescent tube was determined. As a result, the sensitivity change wasobserved on the PS plate (C), but the PS plates (A)-1 to (A)-6 of thepresent invention did not show any change in the sensitivity. In otherwords, it is confirmed that the PS plates of the present invention aresubstantially improved in the white light rays-stability.

EXAMPLES 19 TO 24

Each of light-sensitive solutions which had the same compositions asthose of the light-sensitive solutions (B)-1 to (B)-6 used in Examples 7to 12 except that Oil Blue #603 was removed was applied onto a siliconwafer with a spinner and dried on a hot plate maintained at 90° C. for 2minutes. The thickness of the layer was 1.0 μm.

Then the resultant light-sensitive layer was exposed to light with ascale down projection aligner (stepper) using monochromatic light of 365nm and subjected to post-heating at 90° C. for one minute. Then it wasdeveloped with a 2.4% aqueous solution of tetramethyl ammonium hydroxidefor 60 seconds to form a resist pattern. As a result, a good patternhaving a line & space of 0.7 μm was obtained.

EXAMPLES 25 TO 26

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (E) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (E)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   0.90                                                    Cresol/formaldehyde/novolak resin                                                                   0.70                                                    (m/p-cresol ratio = 6/4)                                                      Ethyl Michler's ketone                                                                              0.06                                                    Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (a)-(30) and(a)-(37) whose weight average molecular weights (GPC: polystyrenestandard) were 3,500 and 5,000 respectively. In these siloxane polymers,the content of the N-oxyamidosulfonate group- or N-oxyimidosulfonategroup-containing siloxane unit was 50 mole % in both cases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 19 to 24 and as a result, a goodpattern having a line & space of 0.7 μm was obtained. Then the layer waetched for 20 minutes with a diode parallel plates reactive ion etchingapparatus under the conditions of 20 mTorr of O₂ gas pressure and 200mW/cm² of RF power. Thus, the pattern of the upper layer was completelytransferred to the lower HPR-204 layer. The resulting resist pattern wascomposed of the upper and lower two layers having a high aspect ratio.

More specifically, it was confirmed that the resist of the inventioncould be used as an upper resist in the two layer resist technique

The light-sensitive composition of the present invention is excellent inboth white light rays-stability and resistance to oxygen plasma, thesensitivity thereof can be enhanced by use of a sensitizer, it can bedeveloped with an alkaline developer and the production thereof is veryeasy.

PREPARATION EXAMPLE 9 Preparation of 2-Nitrobenzyl Acrylate

153.2 g (1.0 mole) of 2-nitrobenzyl alcohol, 95.7 g (0.94 mole) oftriethylamine and 12.9 g (0.11 mole) of 4-(dimethylamino)pyridine weredissolved in 600 ml of acetone and to the resulting solution, there wasdropwise added a solution of 95.0 g (1.05 mole) of acryloyl chloride in150 ml of acetone at 0° C. over one hour with stirring. Then thestirring was continued for additional one hour. After filtering off theresulting salt, the filtrate was concentrated and purified by columnchromatography (packed material: silica gel: eluent: hexane/ethylacetate=10/1). Thus, 141 g of an oily liquid was recovered.

It was confirmed that the liquid was 2-nitrobenzyl acrylate in terms ofNMR spectroscopy.

PREPARATION EXAMPLE 10 Preparation of Exemplified Compound (b)-(32)

87.1 g (0.50 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 103.6 g(0.50 mole) of 2-nitrobenzyl acrylate were dissolved in 1 l of dioxaneand stirred at 100° C. for one hour under heating. After cooling to roomtemperature, 99.1 g (0.50 mole) of trimethoxyphenyl silane was added tothe mixture. Further, 70 ml of distilled water and 0.5 g of concentratedhydrochloric acid were added thereto and the mixture was stirred for 30minutes. Then the solution was heated to remove the solvent (dioxane)and to thus concentrate the solution. The resulting concentrate wasadded to 10 l of water with stirring and the solid precipitated out wasfiltered off and dried in vacuo. Thus, 220 g of a brownish white resinwas obtained. It was confirmed that the resin was exemplified compound(b)-(32) in terms of NMR spectroscopy. In addition, the molecular weightthereof was determined by gel permeation chromatography (GPC) and theweight average molecular weight thereof (polystyrene standard) was foundto be 4,500.

EXAMPLES 27 TO 32

An aluminum substrate was prepared in the same manner used in Examples 1to 6.

Six kinds of light-sensitive solutions (F)-1 to (F)-6 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (F) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (F)-1 to (F)-6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solutions (F)-1 to(F)-6 are listerd in Table III given below.

    ______________________________________                                        Light-sensitive Solution (F)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.50                                                  Cresol/formaldehyde/novolak resin                                                                     1.0                                                   (m/p-cresol ratio = 6/4)                                                      Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Dichloroethane          10                                                    Methyl cellosolve       10                                                    ______________________________________                                    

A gray scale having a density difference of 0.15 was brought in closecontact with the light-sensitive layer of each PS plate (F)-1 to (F)-6and the layer was exposed to light from a 2 KW high pressure mercurylamp at a distance of 50 cm for 2 minutes. The exposed PS plates (F)-1to (F)-6 were immersed in and developed with DF-4 (trade name; availablefrom Fuji Photo Film Co., Ltd.) diluted 8 times with water for 60seconds at 25° C. to thus obtain positive images dyed blue which wasclear and free of indistinctness without forming a coupling product dyedbrown.

Each of the organopolysiloxane compounds of the present invention usedhad a weight average molecular weight (GPC; polystyrene standard)ranging from 2,000 to 10,000.

Moreover, among the siloxane polymers used, exemplified compounds(b)-(32), (b)-(40), (b)-(41) and (b)-(45), the content of thenitrobenzyl ester group- or nitrobenzylsulfonate group-containingsiloxane unit was 50 mole % in each compounds listed above.

                  TABLE III                                                       ______________________________________                                        Ex. No. PS plate siloxane polymer of the invention used                       ______________________________________                                        27      (F)-1    Exemplified Compound (b)-(17)                                28      (F)-2    Exemplified Compound (b)-(26)                                29      (F)-3    Exemplified Compound (b)-(32)                                30      (F)-4    Exemplified Compound (b)-(40)                                31      (F)-5    Exemplified Compound (b)-(41)                                32      (F)-6    Exemplified Compound (b)-(45)                                ______________________________________                                    

EXAMPLES 33 TO 38

Each of light-sensitive solutions (G)-1 to (G)-6 which had the samecompositions as those of the light-sensitive solutions (F)-1 to (F)-6used in Examples 27 to 32 except that Oil Blue #603 was removed wasapplied onto a silicon wafer with a spinner and dried on a hot platemaintained at 90° C. for 2 minutes. The thickness of the layer was 1.0μm.

Then the resultant light-sensitive layer was exposed to light with ascale down projection aligner (stepper) using monochromatic light of 365nm and was developed with a 2.4% aqueous solution of tetramethylammonium hydroxide for 60 seconds to form a resist pattern. As a result,a good pattern having a line & space of 0.7 μm was obtained.

EXAMPLES 39 TO 40

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (H) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (H)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   0.90                                                    Cresol/formaldehyde/novolak resin                                                                   0.70                                                    (m/p-cresol ratio = 6/4)                                                      Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (b)-(32) and(b)-(45) whose weight average molecular weights (GPC; polystyrenestandard) were 4,500 and 6,000 respectively. In these siloxane polymers,the content of the nitrobenzyl ester group- or nitrobenzylsulfonategroup-containing siloxane unit was 50 mole % in both cases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 33 to 38 and as a result, a goodpattern having a line & space of 0.7μm was obtained. Then the layer wasetched for 20 minutes with a diode parallel plates reactive ion etchingapparatus under the conditions of 20 mTorr of O₂ gas pressure and 200mW/cm² of RF power. Thus, the pattern of the upper layer was completelytransferred to the lower HPR-204 layer. The resulting resist pattern wascomposed of the upper and lower two layers having a high aspect ratio.

More specifically, it was confirmed that the resist of the inventioncould be used as an upper resist in the two layer resist technique.

The light-sensitive compositions of the present invention do notgenerate gases during exposure to light and do not undergo any couplingreaction during development. Moreover, they are excellent in resistanceto oxygen plasma and can easily be produced.

PREPARATION EXAMPLE 11 Preparation of 3,5-Dimethoxybenzyl Alcohol

7.6 g of lithium aluminum hydride (LiAlH₄) was dispersed in 100 ml ofdehydrized and dried tetrahydrofuran (THF). To the resulting dispersion,there was dropwise added a solution of 36.4 g of 3,5-dimethoxy benzoatein 200 ml of dehydrized THF over one hour with stirring. Subsequently,the stirring was continued at room temperature for additional one hour.After 20 ml of water was dropwise added to treat the remaining LiAlH₄,this reaction added to 1.5 l of water. The reaction mixture wasacidified by addition of 20 g of conc. hydrochloric acid and extractedtwice with 700 ml of ethyl acetate. The extract was washed with waterand then dried over anhydrous magnesium sulfate. The dried ethyl acetatesolution was concentrated and purified by column chromatography (packedmaterial: silica gel; eluent: hexane/ethyl acetate=2/1) to give 31 g ofcolorless needles. It was confirmed that the crystals obtained were3,5-dimethoxybenzyl alcohol in terms of NMR spectroscopy: ##STR46##

PREPARATION EXAMPLE 12 Preparation of 3,5-Dimethoxybenzyl Acrylate

16.8 g (0.100 mole) of 3,5-dimethoxybenzyl alcohol, 9.5 g (0.094 mole)of triethylamine and 1.3 g (0.011 mole) of 4-(dimethylamino) pyridinewere dissolved in 120 ml of acetone. To the resulting solution, therewas dropwise added a solution of 9.5 g (0.105 mole) of acryloyl chloridein 30 ml of acetone at room temperature over 30 minutes with stirring.Subsequently, the stirring was continued for additional one hour. Thesalt formed was filtered off, the filtrate was concentrated and purifiedby column chromatography (packed material: silica gel; eluent:hexane/ethyl acetate=5/1) to give 15.2 g of an oily liquid.

It was confirmed that the product obtained was 3,5-dimethoxybenzylacrylate in terms of NMR spectroscopy: ##STR47##

PREPARATION EXAMPLE 13 Preparation of Exemplified Compound (c)-(36)

8.8 g (0.05 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 12.0 g (0.05mole) of phenyl triethoxysilane were dissolved in 100 ml of dioxane,further 10 ml of distilled water and 0.1 g of conc. hydrochloric acidwere added to the solution and the resulting mixture was stirred for 30minutes. Then the solvents, dioxane and water were distilled off underheating to concentrate the mixture. The concentrate was redissolved in80 ml of dioxane, 11.1 g (0.05 mole) of 3,5-dimethoxybenzyl acrylate wasadded to the solution and the mixture was heated at 100° C. for one hourwith stirring. The reaction solution was added to 1 l of water withstirring, the precipitates formed was filtered off and dried in vacuo.Thus, 20.5 g of a white resin was obtained. It was confirmed that theresin was compound (c)-(36) in terms of NMR spectroscopy. In addition,the molecular weight thereof was determined by gel permeationchromatography (GPC) and the weight average molecular weight(polystyrene standard) thereof was found to be 3,600.

EXAMPLES 41 TO 46

Six kinds of light-sensitive solutions (I)-1 to (I)-6 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (I) having the following composition. Each ofthese light-sensitive solutions was applied onto a silicon wafer with aspinner and dried on a hot plate maintained at 90° C. for 2 minutes. Thethickness of the resulting film was 1.0μ.

    ______________________________________                                        Light-sensitive Solution (I)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   0.50                                                    Cresol/formaldehyde/novolak resin                                                                   1.0                                                     (m/p-cresol ratio = 6/4)                                                      Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers used in the light-sensitive solutions (I)-1 to(I)-6 are listerd in Table IV given below.

The resulting resist layer was exposed to pulsed light from a KrFexcimer laser of 249 nm through a mask and developed with a 2.4% aqueoussolution of tetramethyl ammonium hydroxide for 60 seconds to thus form aresist pattern. As a result, a good pattern having a line & space of 0.4μm.

                  TABLE IV                                                        ______________________________________                                        Ex. No. PS plate siloxane polymer of the invention used                       ______________________________________                                        41      (I)-1    Exemplified Compound (c)-(16)                                42      (I)-2    Exemplified Compound (c)-(25)                                43      (I)-3    Exemplified Compound (c)-(32)                                44      (I)-4    Exemplified Compound (c)-(36)                                45      (I)-5    Exemplified Compound (c)-(46)                                46      (I)-6    Exemplified Compound (c)-(51)                                ______________________________________                                    

Each of the siloxane polymers of the present invention used had a weightaverage molecular weight (GPC; polystyrene standard) ranging from 2,800to 4,500. Moreover, among the siloxane polymers used, exemplifiedcompounds (c)-(32), (c)-(36), (c)-(46) and (c)-(51), the content of thealkoxybenzyl ester group- or alkoxybenzylsulfonate group-containingsiloxane unit was 50 mole % in each compounds listed above.

EXAMPLES 47 TO 48

A commercially available novolak type resist HFR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (J) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (J)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   1.0                                                     Cresol/formaldehyde/novolak resin                                                                   0.60                                                    (m/p-cresol ratio = 6/4)                                                      Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (c)-(34) and(c)-(45) whose weight average molecular weights (GPC; polystyrenestandard) were 3,500 and 3,200 respectively. In these siloxane polymers,the content of the alkoxybenzyl ester group- or alkoxybenzylsulfonategroup-containing siloxane unit was 25 mole % in both cases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 41 to 46 and as a result, a goodpattern having a line & space of 0.4 μm was obtained. Then the layer wasetched for 20 minutes with a diode parallel plates reactive ion etchingapparatus under the conditions of 20 mTorr of O₂ gas pressure and 200mW/cm² of RF power. Thus, the pattern of the upper layer was completelytransferred to the lower HPR-204 layer. The resulting resist pattern wascomposed of the upper and lower two layers having a high aspect ratio.

More specifically, it was confirmed that the resist of the inventioncould be used as an upper resist in the two layer resist technique.

PREPARATION EXAMPLE 14 Preparation of vinyl-1-naphthyl Disulfone##STR48##

189 g of sodium sulfite was dissolved in 600 ml of water, the solutionwas warmed at a temperature ranging from 60° to 70° C., 68 g of1-naphthalenesulfonyl chloride was added and then the mixture wasreacted at a temperature ranging from 50° to 60° C. for 5 hours.Insolubles were filtered off, the temperature of the reaction solutionwas brought back to room temperature and the solution was acidified byaddition of conc. hydrochloric acid. The resulting precipitates werecollected by filtration to give 55 g of 1-naphthalene sulfinic acid.

15 ml of water was added to 9.6 g of 1-naphthalene sulfinic acid and asolution of 2 g of sodium hydroxide in 5 ml of water was added to themixture. To the solution there was added a solution of 6.3 g ofvinylsulfonyl chloride in 20 ml of acetonitrile at room temperature withstirring and the mixture was stirred at room temperature for additional24 hours. The reaction solution was poured into 300 ml of water, theresulting precipitates were recovered through filtration andrecrystallized from a mixed solvent of benzene and ethanol to give 3.5 gof vinyl-1-naphthyldisulfone.

PREPARATION EXAMPLE 15 Preparation of 4-Tolyl-4-styryldisulfone##STR49##

The same procedures used in Preparation Example 14 were repeated toobtain 45 g of p-toluenesulfinic acid except that 57 g ofp-toluenesulfonyl chloride was substituted for 1-naphthalenesulfonylchloride used in Preparation Example 14.

15 ml of water was added to 7.8 g of p-toluenesulfinic acid and asolution of 2 g of sodium hydroxide in 5 ml of water was added to themixture. To the solution there was added a solution of 10.1 g ofp-styrenesulfonyl chloride in 20 ml of acetonitrile at room temperaturewith stirring and the mixture was stirred at room temperature foradditional 24 hours. The reaction solution was poured into 300 ml ofwater, the resulting precipitates were recovered through filtration andrecrystallized from a mixed solvent of benzene and ethanol to give 5.1 gof 4-tolyl-4-styryldisulfone.

PREPARATION EXAMPLE 16 Preparation of2-Methyl-3-vinylsulfonyloxy-4-(3H)-quinazoline ##STR50##

11.8 g of hydroxylamine hydrochloride was dissolved in 20 ml of waterand 65 ml of a 20% by weight sodium hydroxide aqueous solution was addedto the solution. 50 ml of the resulting solution was added to a solutionof 9.7 g of methyl N-acetylanthranilate in 40 ml of methanol and themixture was stirred at room temperature for 48 hours. After removal ofthe solvent under reduced pressure, 100 ml of water was added to theresidue to dissolve it, 5 ml of conc. hydrochloric acid was addedthereto, the crystals precipitated out was recovered by filtration andrecrystallized from an ethanol/water mixed solvent to give 7.5 g of2-methyl-3-hydroxy-4(3H)-quinazoline.

4.4 g of 2-methyl-3-hydroxy-4(3H)-quinazoline and 3.2 g of vinylsulfonylchloride were added to 50 ml of acetone and 2.8 g of triethylamine wasdropwise added to the solution with stirring while maintaining thetemperature of the solution at 0° to 20° C. Further, the stirring wascontinued at 20° to 30° C. for additional 3 hours and then the solventwas removed under reduced pressure. 100 ml of water was added to theresidue, the resulting precipitates were collected by filtration andrecrystallized from an ethanol/benzene mixed solvent to give 5.3 g of2-methyl-3-vinylsulfonyloxy™4(3H)-quinazoline.

PREPARATION EXAMPLE 17 Preparation of1,2,3-Triaza-3-(4-styryl)-sulfonyloxy-4-tetralone ##STR51##

To a solution of 26 g of N-hydroxy-2-aminobenzamide and 45 ml of 35%hydrochloric acid in 800 ml of water, there was added a solution of 12.5g of sodium nitrite in 120 ml of water at 50° C. and then stirring wascontinued at room temperature. The resulting precipitates were filteredoff and recrystallized from methanol to give 19.7 g of the followingproduct: ##STR52##

The product was dissolved in 150 ml of tetrahydrofuran (THF) and 12.2 gof triethylamine was added to the solution. To the solution, there wasdropwise added, at 10° C., 24.3 g of p-styrenesulfonyl chloride and themixture was stirred at room temperature for additional one hour.Thereafter, 500 ml of ethyl acetate was added, the mixture was washedwith water and the ethyl acetate solution was dried over Na₂ SO₄. Theethyl acetate solution was concentrated to dryness, the resulting whitesolids were redissolved in acetone and the solution was poured into 4 lof water to give 28.5 g of1,2,3-triaza-3-(4-styryl)-sulfonyloxy-4-tetralone.

PREPARATION EXAMPLE 18 Preparation of Exemplified Compound (d)-(31)

4.4 g (0.025 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 18.0 g(0.075 mole) of phenyl triethoxysilane were dissolved in 100 ml ofdioxane, further 10 ml of distilled water and 0.1 g of conc.hydrochloric acid were added to the solution and the mixture was stirredfor 30 minutes. Then the mixture was concentrated by heating it anddistilling off the solvent. After redissolving the concentrate byaddition of 80 ml of dioxane, 6.6 g (0.025 mole) of2-methyl-3-vinylsulfonyloxy-4(3H)-quinazolinone was added to thesolution and the mixture was heated at 100° C. for one hour withstirring. The reaction solution was poured into 1 l of water withstirring, the resulting precipitates were filtered off and dried invacuo. Thus, 17 g of a brownish white resin was obtained. It wasconfirmed that the resin was exemplified compound (d)-(31) by means ofNMR spectroscopy. In addition, the molecular weight thereof wasdetermined by gel permeation chromatography (GPC) and the weight averagemolecular weight (polystyrene standard) thereof was found to be 3,000.

PREPARATION EXAMPLE 19 Preparation of Exemplified Compound (d)-(33)

The same reaction and post-treatments as used in Preparation Example 18were repeated except that 7.1 g (0.025 mole) ofvinyl-1-naphthyldisulfone was substituted for2-methyl-3-vinylsulfonyloxy-4(3H)-quinazoline used in PreparationExample 18 to obtain 18.5 g of a white resin. It was confirmed that theresin was exemplified compound (d)-(33) by means of NMR spectroscopy. Inaddition, the weight average molecular weight (GPC; polystyrenestandard) thereof was found to be 3,800.

EXAMPLES 49 TO 52

An aluminum substrate was prepared in the same manner as in Examples 1to 6.

Four kinds of light-sensitive solutions (K)-1 to (K)-4 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (K) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (K)-1 to (K)-4. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solutions (K)-1 to(K)-4 are listed in Table V given below.

    ______________________________________                                        Light-sensitive Solution (K)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.50                                                  Cresol/formaldehyde/novolak resin                                                                     1.0                                                   (m/p-cresol ratio = 6/4)                                                      Ethyl Michler's ketone  0.05                                                  Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Mehtyl cellosolve       15                                                    ______________________________________                                    

A gray scale having a density difference of 0.15 was brought in closecontact with the light-sensitive layer of each PS plate (K)-1 to (K)-4and the layer was exposed to light from a 2 KW high pressure mercurylamp at a distance of 50 cm for 2 minutes. The exposed PS plates (K)-1to (K)-4 were immersed in and developed with DP-4 (trade name; availablefrom Fuji Photo Film Co., Ltd.) diluted 8 times with water for 60seconds at 25° C. to thus obtain positive images dyed clear blue.

Each of the siloxane polymers of the present invention used had a weightaverage molecular weight (GPC; polystyrene standard) ranging from 2,500to 4,000.

Moreover, among the siloxane polymers used, exemplified compounds(d)-(40) and (d)-(46), the content of the disulfone group- or3-sulfonyloxy-4-quinazoline group-containing siloxane unit was 25 mole %in each compound.

                  TABLE V                                                         ______________________________________                                        Ex. No. PS plate siloxane polymer of the invention used                       ______________________________________                                        49      (K)-1    Exemplified Compound (d)-(20)                                50      (K)-2    Exemplified Compound (d)-(27)                                51      (K)-3    Exemplified Compound (d)-(40)                                52      (K)-4    Exemplified Compound (d)-(46)                                ______________________________________                                    

EXAMPLES 53 TO 56

A comparative PS plate (L) was prepared in the same manner used inExamples 49 to 52 except that a light-sensitive solution (L) was used.The light-sensitive solution (L) was prepared by using 0.40 g of1,2-naphthoquinonediazido-5-sulfonate of m-cresol/formaldehyde/novola kresin in place of the siloxane polymer of the invention and ethylMichler's ketone in the light-sensitive solution (K). The coated amountof the light-sensitive solution was 1.5 g/m² (weighed after drying).

The PS plates (K)-1 to (K)-4 prepared in Examples 49 to 52 and the PSplate (L) were allowed to stand under irradiation with light rays from awhite fluorescent tube for 20 minutes. These PS plates were exposed tolight and developed in the same manner used in Examples 49 to 52 and thechange in sensitivity thereof observed before and after the irradiationwith the light rays from the white fluorescent tube was determined. As aresult, the sensitivity change was observed on the PS plate (L), but thePS plates (K)-1 to (K)-4 of the present invention did not show anychange in the sensitivity. In other words, it is confirmed that the PSplates of the present invention are substantially improved in the whitelight rays-stability.

EXAMPLES 57 TO 60

Four kinds of light-sensitive solutions (M)-1 to (M)-4 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (M) having the following composition. Each ofthese light-sensitive solutions was applied onto a silicon wafer with aspinner and dried on a hot plate maintained at 90° C. for 2 min. Thethickness of the resulting film was 1.0μ.

    ______________________________________                                        Light-sensitive Solution (M)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   0.50                                                    Cresol/formaldehyde/novolak resin                                                                   1.0                                                     (m/p-cresol ratio = 6/4)                                                      Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers used in the light-sensitive solutions (I)-1 to(I)-6 are listed in Table VI given below.

The resulting resist layer was exposed to pulsed light from a KrFexcimer laser of 249 nm through a mask and developed with a 2.4% aqueoussolution of tetramethyl ammonium hydroxide for 60 seconds to thus form aresist pattern. As a result, a good pattern having a line & space of 0.4μm.

Each of the siloxane polymers of the present invention used had a weightaverage molecular weight (GPC; polystyrene standard) ranging from 3,000to 5,000. Moreover, among the siloxane polymers used, exemplifiedcompounds d)-(31) and d)-(37), the content of the disulfone group- or3-sulfonyloxy-4-quinazoline group-containing siloxane unit was 50 mole %in each compound listed above.

                  TABLE VI                                                        ______________________________________                                        Ex. No. PS plate siloxane polymer of the invention used                       ______________________________________                                        57      (M)-1    Exemplified Compound (d)-(16)                                58      (M)-2    Exemplified Compound (d)-(20)                                59      (M)-3    Exemplified Compound (d)-(31)                                60      (M)-4    Exemplified Compound (d)-(37)                                ______________________________________                                    

EXAMPLES 61 TO 62

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (N) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (N)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   1.00                                                    Cresol/formaldehyde/novolak resin                                                                   0.60                                                    (m/p-cresol ratio = 6/4)                                                      Ethyl Michler's ketone                                                                              0.04                                                    Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (d)-(36) and(d)-(38) whose weight average molecular weights (GPC; polystyrenestandard) were 3,200 and 3,800 respectively. In these siloxane polymers,the content of the disulfone group- or 3-sulfonyloxy-4-quinazolinegroup-containing siloxane unit was 25 mole % in both cases.

The resulting light-sensitive layer was exposed to light with a scaledown projection aligner (stepper) using monochromatic light of 365 nmand developed in the same manner as used in Examples 57 to 60 and as aresult, a good pattern having a line & space of 0.7 μm was obtained.Then the layer was etched for 20 minutes with a diode parallel platesreactive ion etching apparatus under the conditions of 20 mTorr of O₂pressure and 200 mW/cm² of RF power. Thus, the pattern of the upperlayer was completely transferred to the lower HPR-204 layer. Theresulting resist pattern was composed of the upper and lower two layershaving a high aspect ratio.

More specifically, it was confirmed that the resist of the inventioncould be used as an upper resist in the two layer resist technique.

PREPARATION EXAMPLE 20 Preparation of N-t-Butoxycarbonylmaleimide

To a suspension of 9.7 g (0.10 mole) of maleimide and 11.2 g 0.10 mole)of potassium t-butoxide in 200 ml of tetrahydrofuran (THF), there wasdropwise added, at 0° C., 21.8 g (0.10 mole) of di-t-butyldicarbonateover 30 minutes with stirring. Thereafter, the stirring was continuedfor additional one hour. The reaction mixture was poured into 500 ml ofcold water and extracted with ethyl acetate. The crude product obtainedby drying and concentrating the resulting ethyl acetate solution waspurified by column chromatography (packed material: silica gel; eluent:hexane/ethyl acetate) to give 15.8 g of N-t-butoxycarbonylmaleimide.

PREPARATION EXAMPLE 21 Preparation of N-(p-t-Butoxycarbonyloxyphenyl)-maleimide

To a suspension of 18.9 g (0.10 mole) of N-(p-hydroxyphenyl) maleimideand 11.2 g (0.10 mole) of potassium t-butoxide in 200 ml oftetrahydrofuran (THF), there was dropwise added, at 0° C., 21.8 g (0.10mole) of di-t-butyldicarbonate over 30 minutes with stirring.Thereafter, the same reaction and post-treatments as used in PreparationExample 20 were performed to thus give 21.7 g ofN-(p-t-butoxycarbonyloxyphenyl)maleimide.

PREPARATION EXAMPLE 22 Preparation of Exemplified Compound (e)-(32)

8.7 g (0.050 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 9.9 g (0.050mole) of N-t-butoxycarbonyl maleimide were dissolved in 100 m l ofdioxane and heated to 100° C. for one hour with stirring. After coolingto room temperature, 9.9 g (0.050 mole) of trimethoxyphenylsilane wasadded to the solution. Further, 10 ml of distilled water and 0.1 g ofconc. hydrochloric acid were added to the solution and the solution wasstirred for additional 30 minutes. Then the solution was heated toremove the solvent, dioxane, and to concentrate the solution. Theresulting concentrate was added to 1 l of water with stirring, thesolids recipitated out were filtered off and dried in vacuo. Thus, 22.1g of a white resin was obtained. It was confirmed that the resin wasexemplified compound (e)-(32) by means of NMR spectroscopy. In addition,the molecular weight of the compound was determined by gel permeationchromatography (GPC) and the weight average molecular weight(polystyrene standard) thereof was found to be 4,000.

PREPARATION EXAMPLE 23 Preparation of Exemplified Compound (e)-(34)

The same reaction and post-treatments as those used in PreparationExample 22 were performed to obtain 25.5 g of a white resin except that14.5 g (0.050 mole) of N-(p-t-butoxycarbonyloxyphenyl)maleimide wassubstituted for N-t-butoxycarbonyl maleimide used in Preparation Example22. It was confirmed that the resulting resin was exemplified compound(e)-(34) by means of NMR spectroscopy. In addition, the weight averagemolecular weight (GPC: polystyrene standard) thereof was found to be6,000.

PREPARATION EXAMPLE 24 Preparation of Exemplified Compound (e)-(35)

The same reaction and post-treatments as those used in PreparationExample 22 were performed to obtain 18.2 g of a white resin except that6.4 g (0.050 mole) of t-butyl acrylate was substituted forN-t-butoxycarbonyl maleimide used in Preparation Example 22. It wasconfirmed that the resulting resin was exemplified compound (e)-(35) bymeans of NMR spectroscopy. In addition, the weight average molecularweight (GPC; polystyrene standard) thereof was found to be 3,500.

EXAMPLES 63 TO 68

A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10%solution of tertiary sodium phosphate maintained at 80° C. for 3 minutesto degrease the same, grained with a nylon brush, etched with a sodiumaluminate solution for about 10 minutes and then desmutted with a 3%aqueous solution of sodium hydrogen sulfate. The aluminum plate was thenanodized at a current density of 2 A/dm² for 2 minutes in a 20% sulfuricacid solution to thus obtain an aluminum substrate.

Six kinds of light-sensitive solutions (O)-1 to (O)-6 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (O) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (O)-1 to (O)-6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solution (O)-1 to(O)-6 are listed in the following Table VII.

    ______________________________________                                        Light-sensitive Solution (O)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     1.1                                                   PF.sub.6 Salt of triphenylsulfonium                                                                   0.10                                                  Anthracene              0.04                                                  Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Methyl cellosolve       15                                                    ______________________________________                                    

As a comparative example, a PS plate P was prepared by applying thefollowing light-sensitive solution (P) onto the aluminum plate in thesame manner as that described above in connection with thelight-sensitive solution (O). The coated amount of the light-sensitivesolution was 1.5 g/m² (weghed after drying).

    ______________________________________                                        Light-sensitive Solution (P)                                                  Component                  Amount (g)                                         ______________________________________                                        Cresol/formaldehyde/novolak resin                                                                        1.1                                                (m/p-cresol ratio = 6/4)                                                      Condensed product of cresol/formaldehyde/novolak                                                         0.45                                               resin with 1,2-naphthoquinone-2-diazido-5-sulfonyl                            chloride                                                                      2-(p-methoxyphenyl)-4,6-bistrichloromethyl-s-triazine                                                    0.02                                               Oil Blue #603 (available from ORIENT                                                                     0.01                                               CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone        5                                                  Methyl cellosolve          15                                                 ______________________________________                                    

A gray scale having a density difference of 0.15 (step tablet; availablefrom Fuji Photo Film Co., Ltd.) was brought in close contact with thelight-sensitive layer of each PS plate (O)-1 to (O)-6 or (P) and thelayer was exposed to light from a 2 KW high pressure mercury lamp at adistance of 50 cm. After the exposure to light, the PS plates (O)-1 to(O)-6 were heated to 90° C. for one minute. Thereafter, the exposed PSplates (O)-1 to (O)-6 and (P) were immersed in and developed with DP-4(trade name; available from Fuji photo Film Co., Ltd.) diluted 8 timeswith water for 60 seconds at 25° C. and the exposure time required formaking the 5th step of the gray scale having a density difference of0.15 completely clear was determined. The results thus obtained arelisted in the following Table VII.

                  TABLE VII                                                       ______________________________________                                        Ex.                                Exposure                                   No.   PS plate Siloxane Polymer Employed                                                                         Time (sec)                                 ______________________________________                                        63    (O)-1    Exemplified Compound (e)-(21)                                                                     15                                         64    (O)-2    Exemplified Compound (e)-(26)                                                                     20                                         65    (O)-3    Exemplified Compound (e)-(32)                                                                     10                                         66    (O)-4    Exemplified Compound (e)-(34)                                                                      5                                         67    (O)-5    Exemplified Compound (e)-(35)                                                                     15                                         68    (O)-6    Exemplified Compound (e)-(40)                                                                      5                                          1    (P)      Comparative Example 55                                         ______________________________________                                    

As seen from the results listed in Table VII, all the PS plates (O)-1 to(O)-6 in which the siloxane polymers of the invention were used requirea short exposure time and have high sensitivity compared with those forthe comparative PS plate (P).

The weight average molecular weight (GPC; polystyrene standard) of allthe siloxane polymers listed in Table VII range from 3,000 to 8,500.

Moreover, among the siloxane polymers corresponding to exemplifiedcompounds (e)-(32), (e)-(34), (e)-(35) and (e)-(40), the content of thetertiary carbon-ester group- or carboxylate group-containing siloxaneunit was 50 mole % in all the cases.

EXAMPLES 69 TO 74

To examine the stability, with time, of PS plates, the PS plates (O)-1to (O)-6 prepared in Examples 63 to 68 and newly prepared PS plates(Q)-1 and (Q)-2 were kept to stand at a temperature of 45° C. and ahumidity of 75% for 3 days. The PS plates (Q)-1 and (Q)-2 were preparedin the same manner as in Examples 63 to 68 except that the followinglight-sensitive solutiuon (Q) was used (the coated amount of thesolution was 1.5 g/m² weighed after drying).

    ______________________________________                                        Light-sensitive Solution (Q)                                                  Component                 Amount (g)                                          ______________________________________                                        The following silyl ester compound* disclosed in                                                        0.40                                                J. P. KOKAI No. Sho 60-10247                                                  Cresol/formaldehyde/novolak resin                                                                       1.1                                                 (m/p-cresol ratio = 6/4)                                                      2-(p-Methoxyphenyl)-4,6-bistrichloromethyl-                                                             0.05                                                s-triazine                                                                    Oil Blue #603 (available from ORIENT                                                                    0.01                                                CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone       5                                                   Methyl cellosolve         15                                                  ______________________________________                                         *The compounds used in the lightsensitive solution (Q) and disclosed in J     P. KOKAI No. Sho 6010247 are as follows:                                      (Q)1                                                                          ##STR53##                                                                    -  -                                                                           (Q)2                                                                          ##STR54##                                                                

A gray scale having a density difference of 0.15 was brought in closecontact with the light-sensitive layer of each PS plate (O)-1 to (O)-6,(P) or (Q)-1 to (Q)-2 prior to or after allowing to stand under theforegoing conditions and these assembly were exposed to light from a 30A carbon arc lamp at a distance of 70 cm for 30 seconds. Then these PSplates (O)-1 to (O)-6, (P) and (Q)-1 to (Q)-2 were developed in the samemanner as used in Examples 63 to 68 and the difference between thenumber of steps of the gray scale observed on each PS plate before andafter allowing to stand for 3 days under the foregoing conditions (45°C.; 75% humidity) was determined. The results observed are summarized inthe following Table VIII.

                  TABLE VIII                                                      ______________________________________                                        PS plate   difference between the number of steps of the                                 gray scale before and after allowing to stand                                 for 3 days under the conditions (45° C.; 75%                           humidity) (number of steps)                                        (O)-1      0.5                                                                (O)-2      0                                                                  (O)-3      0.5                                                                (O)-4      0                                                                  (O)-5      0                                                                  (O)-6      0                                                                  (P) (Comp. Ex.)                                                                          1.0                                                                (Q)-1 (Comp. Ex.)                                                                        2.5                                                                (Q)-2 (Comp. Ex.)                                                                        1.5                                                                ______________________________________                                    

As seen from Table VIII, all of the PS plates (O)-1 to (O)-6 in whichthe compounds of the present invention were used have the difference inthe step number of the gray scale lower than those for the comparativePS plates (F) and (Q)-1 to (Q)-2 and high stability with time and thusthey are very excellent.

EXAMPLES 75 TO 80

Each of light-sensitive solutions (R)-1 to (R)-6 which had the samecompositions as those of the light-sensitive solutions ((O)-1 to (O)-6used in Examples 63 to 68 except that Oil Blue #603 was removed wasapplied onto a silicon wafer with a spinner and dried on a hot platemaintained at 90° C. for 2 minutes. The thickness of the resulting layerwas 1.0 μm.

Then the resulting light-sensitive layer was exposed to light with ascale down projection aligner (stepper) using monochromatic light of 365nm and subjected to post-heating at 90° C. for one minute. Then it wasdeveloped with a 2.4% aqueous solution of tetramethyl ammonium hydroxidefor 60 seconds to form a resist pattern. As a result, a good patternhaving a line & space of 0.7μm was obtained.

EXAMPLES 81 TO 82

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (S) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (S)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   1.10                                                    PF.sub.6 Salt of diphenyl iodonium                                                                  0.10                                                    Anthracene            0.04                                                    2-Ethoxyethyl acetate 8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (e)-(32) and(e)-(34) whose weight average molecular weights (GPC; polystyrenestandard) were 4,000 and 6,500 respectively. In these siloxane polymers,the content of the tertiary carbon-ester group- or carbonate estergroup-containing siloxane unit was 50% in both cases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 75 to 80 and as a result, a goodpattern having a line & space of 0.7 μm was obtained. Then the layer wasetched for 20 minutes with a diode parallel plates reactive ion etchingapparatus under the conditions of 20 mTorr of O₂ gas pressure and 200mW/cm² of RF power. Thus the pattern of the upper layer was completelyor faithfully transferred to the lower HPR-204 layer. The resultingresist pattern was composed of the upper and lower two layers having ahigh aspect ratio.

More specifically, it was confirmed that the resist of the presentinvention could be used as an upper resist in the two layer resisttechnique.

The light-sensitive composition of the present invention is highlysensitive, is excellent in stability with time and resistance to oxygenplasma, can be developed with an alkaline developer and can easily beprepared.

PREPARATION EXAMPLE 25 Preparation of Exemplified Compound (f)-(34)

8.7 g (0.050 mole) of 2-(trimethoxysilyl -1,3-butadiene and 9.5 g (0.050mole) of N-(p-hydroxyphenyl)maleimide were dissolved in 100 ml ofdioxane and the solution was heated to 100° C. for one hour withstirring. After cooling to room temperature, 9.9 g (0.050 mole) oftrimethoxyphenylsilane was added to the solution. Further, 10 ml ofdistilled water and 0.1 g of conc. hydrochloric acid were added to thesolution and it was stirred for 30 minutes. Thereafter, the solution washeated to remove the solvent and to thus concentrate the solution. Theconcentrate was added to 1 l of water with stirring, the resultingprecipitates were filtered off and dried in vacuo. Thus, 22.4 g of awhite resin was obtained.

The resin was redissolved in 100 ml of dioxane, then 3.4 g (0.050 mole)of imidazole was added to the solution and a solution of 5.5 g (0.050mole) of trimethyl chlorosilane in 20 ml of dioxane was dropwise addedto the solution over 30 minutes. Then the solution was continuouslystirred at room temperature for 24 hours. The resulting imidazolehydrochloride was filtered off and the reaction solution was added to 2l of water with stirring. The precipitates formed were filtered off anddried in vacuo to give 24.5 g of a white resin.

It was confirmed that the resin was exemplified compound (f)-(34) bymeans of NMR spectroscopy. In addition, the molecular weight of theresin was also determined by gel permeation chromatography (GPC) and theweight average molecular weight (polystyrene standard) thereof was foundto be 5,300.

PREPARATION EXAMPLE 26 Preparation of Exemplified Compound (f)-(36)

8.7 g (0.050 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 9.9 g (0.050mole) of trimethoxyphenylsilane were dissolved in 100 ml of dioxane,further 10 ml of distilled water and 0.1 g of conc. hydrochloric acidwere added to the solution and it was stirred for 30 minutes.Thereafter, the solution was heated to remove the solvent and to thusconcentrate the solution. The concentrate was added to 1 l of water withstirring, the resulting solids were filtered off and dried in vacuo.Thus, 13.4 g of a white resin was obtained. The resin was redissolved in100 ml of dioxane, then 9.3 g (0.050 mole) of t-butyldimethylsilylacrylate was added to the solution and it was heated to 100° C. for onehour with stirring. The reaction solution was concentrated and theresulting concentrate was added to 2 l of water with stirring. Theprecipitates formed were filtered off and dried in vacuo to give 22.0 gof a white resin. It was confirmed that the resin was exemplifiedcompound (f)-(36) by means of NMR spectroscopy. In addition, themolecular weight of the resin was also determined by GPC and the weightaverage molecular weight polystyrene standard) thereof was found to be4,500.

PREPARATION EXAMPLE 27 Preparation of Exemplified Compound (f)-(33)

The same reaction and post-treatments as those used in PreparationExample 26 except that 16.6 g (0.050 mole) ofN-(p-t-butyldimethylsiloxycarbonylphenyl)maleimide was substituted fort-butyldimethylsilyl acrylate used in Preparation Example 26 to thusgive 29.2 g of a white resin. It was confirmed that the resin wasexemplified compound (f)-(33) by means of NMR spectroscopy. In addition,the molecular weight of the resin was also determined by GPC and theweight average molecular weight polystyrene standard) thereof was foundto be 5,000.

EXAMPLES 83 TO 88

A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10%solution of tertiary sodium phosphate maintained at 80° C. for 3 minutesto degrease the same, grained with a nylon brush, etched with a sodiumaluminate solution for about 10 minutes and then desmutted wit a 3%aqueous solution of sodium hydrogen sulfate. The aluminum plate was thenanodized at a current density of 2 A/dm² for 2 minutes in a 20% sulfuricacid solution to thus obtain an aluminum substrate.

Six kinds of light-sensitive solutions (T)-1 to (T)-6 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (T) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (T)-1 to (T)-6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solution (T)-1 to(T)-6 are listed in the following Table IX.

    ______________________________________                                        Light-sensitive Solution (T)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.50                                                  Cresol/formaldehyde/novolak resin                                                                     1.0                                                   (m/p-cresol ratio = 6/4)                                                      PF.sub.6 Salt of triphenylsulfonium                                                                   0.05                                                  Anthracene              0.02                                                  Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Methyl cellosolve       15                                                    ______________________________________                                    

As a comparative example, a PS plate U was prepared by applying thefollowing light-sensitive solution (U) onto the aluminum plate in thesame manner as that described above in connection with thelight-sensitive solution (T). The coated amount of the light-sensitivesolution was 1.5 g/m² (weighed after drying).

    ______________________________________                                        Light-sensitive Solution (U)                                                  Component                  Amount (g)                                         ______________________________________                                        Cresol/formaldehyde/novolak resin                                                                        1.1                                                (m/p-cresol ratio = 6/4)                                                      Condensed product of cresol/formaldehyde/novolak                                                         0.45                                               resin with 1,2-naphthoquinone-2-diazido-5-sulfonyl                            chloride                                                                      2-(p-methoxyphenyl)-4,6-bistrichloromethyl-s-triazine                                                    0.02                                               Oil Blue #603 (available from ORIENT                                                                     0.01                                               CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone        5                                                  Methyl cellosolve          15                                                 ______________________________________                                    

A gray scale having a density difference of 0.15 (step tablet; availablefrom Fuji Photo Film Co., Ltd. was brought in close contact with thelight sensitive layer of each PS plate (T)-1 to (T)-6 or (U) and thelayer was exposed to light from a 2 KW high pressure mercury lamp at adistance of 50 cm. Thereafter, the exposed PS plates (T)-1 to (T)-6 and(U) were immersed in and developed with DP-4 (trade name; available fromFuji Photo Film Co., Ltd.) diluted 8 times with water for 60 seconds at25° C. and the exposure time required for making the 5th step of thegray scale having a density difference of 0.15 completely clear wasdetermined. The results thus obtained are listed in the following TableIX.

                  TABLE IX                                                        ______________________________________                                                                           Exposure                                   Ex. No.                                                                              PS plate Siloxane Polymer Employed                                                                        Time (sec)                                 ______________________________________                                        83     (T)-1    Exemplified Compound (f)-(25)                                                                    20                                         84     (T)-2    Exemplified Compound (f)-(26)                                                                    35                                         85     (T)-3    Exemplified Compound (f)-(34)                                                                    15                                         86     (T)-4    Exemplified Compound (f)-(35)                                                                    25                                         87     (T)-5    Exemplified Compound (f)-(37)                                                                    30                                         88     (T)-6    Exemplified Compound (f)-(40)                                                                    20                                          2     (U)      Coompartive Example                                                                              55                                         ______________________________________                                    

As seen from the results listed in Table IX, all the PS plates (T)-1 to(T)-6 in which the siloxane polymers of the invention were used requirea short exposure time and have high sensitivity compared with those forthe comparative PS plate (U).

The weight average molecular weight (GPC; polystyrene standard) of allthe siloxane polymers listed in Table IX range from 4,000 to 7,500.

Moreover, in the siloxane polymers corresponding to exemplifiedcompounds (f)-(34), (f)-(35), (f)-(37) and (f)-(40), the content of thesilyl ether group- or silyl ester group-containing siloxane unit was 50mole % in all the cases.

EXAMPLES 89 TO 94

Each of light-sensitive solutions which had the same compositions asthose of the light-sensitive solutions (T)-1 to (T)-6 used in Examples83 to 88 except that Oil Blue #603 was removed was applied onto asilicon wafer with a spinner and dried on a hot plate maintained at 90°C. for 2 minutes. The thickness of the resulting layer was 1.0 μm.

Then the resulting light-sensitive layer was exposed to light with ascale down projection aligner (stepper) using monochromatic light of 365nm and then it was developed with a 2.4% aqueous solution of tetramethylammonium hydroxide for 60 seconds to form a resist pattern. As a result,a good pattern having a line & space of 0.7 μm was obtained.

EXAMPLES 95 TO 96

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (X) was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (X)                                                  Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   0.90                                                    Cresol/formaldehyde/novolak resin                                                                   0.70                                                    (m/p-cresol ratio = 6/4)                                                      PF.sub.6 Salt of diphenyl iodonium                                                                  0.10                                                    Anthracene            0.04                                                    Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (f)-(34) andf)-(37) whose weight average molecular weights (GPC; polystyrenestandard) were 5,300 and 4,500 respectively. In these siloxane polymers,the content of the silyl ether group- or silyl ester group-containingsiloxane unit was 50% in both cases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 89 to 94 and as a result, a goodpattern having a line & space of 0.7 μm was obtained. Then the layer wasetched for 20 minutes with a diode parallel plates reactive ion etchingapparatus under the conditions of 20 mTorr of O₂ gas pressure and 200mW/cm² of RF power. Thus the pattern of the upper layer was completelyor faithfully transferred to the lower HPR-204 layer. The resultingresist pattern was composed of the upper and lower two layers having ahigh aspect ratio.

More specifically, it was confirmed that the resist of the presentinvention could be used as an upper resist in the two layer resisttechnique.

The light-sensitive composition of the present invention is highlysensitive, is excellent in resistance to oxygen plasma, can be developedwith an alkaline developer and can easily be prepared.

PREPARATION EXAMPLE 28 Preparation of Exemplified Compound (g)-(30)

8.7 g (0.05 mole) of 2-(trimethoxysilyl)-1,3-butadiene and 5.7 g (0.05mole) of N-hydroxymaleimide were dissolved in 100 m of dioxane and theresulting solution was stirred at 100° C. for one hour. After cooling toroom temperature, 9.9 g (0.05 mole) of trimethoxyphenyl-silane was addedto the solution. Further, 10 ml of distilled water and 0.1 g of conc.hydrochloric acid were added thereto and the solution was stirred for 30minutes. Thereafter, the solution was heated to remove the solvent,dioxane, and to thus concentrate the solution. The concentrate was addedto 1 l of water with stirring, the solids precipitated out were filteredoff and dried in vacuo. Thus, 18.2 g of a brownish white resin wasrecovered. It was confirmed that the resin was exemplified compound(g)-(30) (D=H) by means of NMR spectroscopy.

The resin was redissolved in 100 ml of γ-butyrolactone and 13.4 g (0.050mole) of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride was added tothe resulting solution. To the solution, there was dropwise added 5.1 g0.050 mole) of triethylamine over 20 minutes. Then 15 ml of water wasadded and the pH value of the solution was adjusted to about 6.5 bydropwise addition of additional triethylamine. The reaction mixture wasadded to 3 l of water with stirring. The resin precipitated out wasfiltered off and dried in vacuo to give 26.5 g of a yellow resin(exemplified compound (g)-(30);D=1,2-naphthoquinone-2-diazido-5-sulfonyl group).

The molecular weight of the resin was determined by gel permeationchromatography (GPC) and the weight average molecular weight(polystyrene standard) thereof was found to be 4,800.

PREPARATION EXAMPLE 29 Preparation of Exemplified Compound (g)-(32)

The same reaction and post-treatments as used in Preparation Example 28were performed except that 5.1 g (0.050 mole) ofN-hydroxy-N-methylacrylamide was substituted for N-hydroxymaleimide usedin Preparation Example 28 to thus obtain 24.8 g of a yellow resin. Themolecular weight of the resulting resin was determined by GPC and theweight average molecular weight polystyrene standard) thereof was foundto be 3,800.

PREPARATION EXAMPLE 30 Preparation of Exemplified Compound (g)-(34)

The same reaction and post-treatments as used in Preparation Example 28were performed except that 8.2 g (0.050 mole) ofN-(p-hydroxyphenyl)acrylamide was substituted for N-hydroxymaleimideused in Preparation Example 28 to thus obtain 29.2 g of a yellow resin.The molecular weight of the resulting resin was determined by GPC andthe weight average molecular weight (polystyrene standard) thereof wasfound to be 5,500.

EXAMPLES 96 TO 102

A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10%aqueous solution of tertiary sodium phosphate maintained at 80° C. for 3minutes to degrease the same, grained with a nylon brush, etched with asodium aluminate solution for about 10 minutes and then desmutted with a3% aqueous solution of sodium hydrogen sulfate. The aluminum plate wasthen anodized at a current density of 2 A/dm² for 2 minutes in a 20%sulfuric acid solution to thus obtain an aluminum substrate.

Six kinds of light-sensitive solutions (Y)-1 to (Y)-6 were prepared bychanging the kinds of siloxane polymers of the present invention used ina light-sensitive solution (Y) having the following composition. Each ofthese light-sensitive solutions was applied onto the aluminum plate,which had been anodized, and dried at 100° C. for 2 minutes to obtainthe corresponding PS plates (Y)-1 to (Y)-6. The coated amount of thelight-sensitive solution was 1.5 g/m² (weighed after drying) in all thePS plates.

The siloxane polymers used in the light-sensitive solution (Y)-1 to(Y)-6 are listed in the following Table X.

    ______________________________________                                        Light-sensitive Solution (Y)                                                  Component               Amount (g)                                            ______________________________________                                        Siloxane polymer of the invention                                                                     0.70                                                  Cresol/formaldehyde/novolak resin                                                                     1.0                                                   (m/p-cresol ratio = 6/4)                                                      Oil Blue #603 (available from ORIENT                                                                  0.02                                                  CHEMICAL INDUSTRIES CO., LTD.)                                                Methyl ethyl ketone     5                                                     Methyl cellosolve       15                                                    ______________________________________                                    

A gray scale having a density difference of 0.15 was brought in closecontact with the light-sensitive layer of each PS plate (Y)-1 to (Y)-6and the layer was exposed to light from a 2 KW high pressure mercurylamp for one minute at a distance of 50 cm. Thereafter, the exposed PSplates (Y)-1 to Y)-6 were immersed in and developed with DP-4 (tradename; available from Fuji Photo Film Co., Ltd.) diluted 8 times withwater for 60 seconds at 25° C. Thus, there was obtained an image dyedclear blue.

The weight average molecular weight (GPC; polystyrene standard) of allthe siloxane polymers used in these Examples range from 3,000 to 7,000.

Moreover, in the siloxane polymers corresponding to exemplifiedcompounds (g)-(30), (g)-(32), (g)-(34) and (g)-(44), the content of thestructural unit derived from phenolic OH group-, N-hydroxylamido group-or N-hydroxylimino group-containing siloxane was 50 mole % on the basisof the total amount of the charge stock in all the cases.

                  TABLE X                                                         ______________________________________                                        Ex. No.   PS plate Siloxane Polymer Employed                                  ______________________________________                                         97       (Y)-1    Exemplified Compound (g)-(17)                               98       (Y)-2    Exemplified Compound (g)-(19)                               99       (Y)-3    Exemplified Compound (g)-(30)                              100       (Y)-4    Exemplified Compound (g)-(32)                              101       (Y)-5    Exemplified Compound (g)-(34)                              102       (Y)-6    Exemplified Compound (g)-(44)                              ______________________________________                                    

EXAMPLES 103 TO 108

Each of light-sensitive solutions (Y')-1 to (Y')-6 which had the samecompositions as those of the light-sensitive solutions (Y)-1 to (Y)-6used in Examples 97 to 102 except that Oil Blue #603 was removed wasapplied onto a silicon wafer with a spinner and dried on a hot platemaintained at 90° C. for 2 minutes. The thickness of the resulting layerwas 1.0 μm.

Then the resulting light-sensitive layer was exposed to light with ascale down projection aligner (stepper) using monochromatic light of 436nm and then it was developed with a 2.4% aqueous solution of tetramethylammonium hydroxide for 60 seconds to form a resist pattern. As a result,a good pattern having a line & space of 0.8 μm was obtained.

EXAMPLES 109 TO 110

A commercially available novolak type resist HPR-204 (available fromFuji Hunt Chemical Co., Ltd.) was applied onto a silicon wafer with aspinner and dried at 220° C. for one hour to obtain an underlyingcoating. The thickness thereof was 2.0 μm.

The following light-sensitive solution (C') was applied onto theunderlying layer with a spinner and dried on a hot plate maintained at90° C. for 2 minutes to form a coated film having a thickness of 0.5 μm.

    ______________________________________                                        Light-sensitive Solution (C')                                                 Component             Amount (g)                                              ______________________________________                                        Siloxane polymer of the invention                                                                   1.00                                                    Cresol/formaldehyde/novolak resin                                                                   0.60                                                    (m/p-cresol ratio = 6/4)                                                      Ethyl cellosolve acetate                                                                            8.5                                                     ______________________________________                                    

The siloxane polymers of the invention used in these Examples weresiloxane polymers corresponding to exemplified compounds (g)-(30) and(g)-(34) whose weight average molecular weights (GPC; polystyrenestandard) were 4,800 and 5,500 respectively. In these siloxane polymers,the content of the structural unit derived from the N-hydroxylimidogroup- or phenolic OH group-containing siloxane unit was 50% in bothcases.

The resulting light-sensitive layer was exposed to light and developedin the same manner as used in Examples 103 to 108 and as a result, agood pattern having a line & space of 0.8 μm was obtained. Then thelayer was etched for 20 minutes with a diode parallel plates reactiveion etching apparatus under the conditions of 20 mTorr of O₂ gaspressure and 200 mW/cm² of RF power. Thus, the pattern of the upperlayer was completely or faithfully transferred to the lower HPR-204layer. The resulting resist pattern was composed of the upper and lowertwo layers having a high aspect ratio.

More specifically, it was confirmed that the resist of the presentinvention could be used as an upper resist in the two layer resisttechnique.

The light-sensitive composition of the present invention is excellent infilm-forming ability, solubility in solvents and resistance to oxygenplasma, can be developed with an alkaline developer and can easily beprepared.

What is claimed is:
 1. A siloxane polymer having at least 1 mol % of arepeating unit obtained by hydrolysis or alkoxylation followed bycondensation of a cyclic heat addition product between a diene compoundof formula (I) or (II) and an olefin or acetylene compound having aphenolic OH, N-hydroxyamide, N-hydroxyimide or anilino group of formula(III), (IV) or (V): ##STR55## wherein R¹ to R⁵ may be the same ordifferent and represent hydrogen atoms, alkyl, aryl or alkoxy groups;R⁶to R⁹ may be the same or different and represent hydrogen or halogenatoms, cyano, alkyl, aryl, alkoxy, --SO₂ R¹², --SO₃ R¹², --CO--R¹²,--CO--NH--R¹², --COO--R¹², or --Y--A, wherein R¹² represents an alkyl oraryl group; R¹⁰ and R¹¹ represent hydrogen atoms, alkyl or aryl groups;Y represents a single bond, a divalent aromatic or aliphatic hydrocarbongroup; A represents --OH, ##STR56## wherein R⁵¹³ and R⁵¹⁴ may be thesame or different and represent hydrogen or halogen atoms, cyano, nitro,alkyl, aryl, alkoxy, --CO--R⁵¹⁵, --COO--R⁵¹⁵, --O--CO--R⁵¹⁵,--NHCO--R⁵¹⁵, --CONH--R⁵¹⁵, --NH--CONH--R⁵¹⁵, --NHCOO--R⁵¹⁵ or--OCONH--R⁵¹⁵, wherein R⁵¹⁵ represents an alkyl or aryl group; Brepresents a divalent alkylene or arylene group; a represents an integerof 1 to 3; X¹, X² and X³ may be the same or different and representhalogen atoms, hydroxy, carboxy, oxime, amide, ureido, amino, alkyl,aryl, aralkyl, alkoxy, aryloxy, ##STR57## provided that at least two ofX¹, X² and X³ are halogen atoms, hydroxy, carboxy, oxime, amide, ureido,amino, alkoxy or aryloxy groups and two of R⁶ to R⁸ and Y, R¹⁰ and R¹¹may combine to form a ring.
 2. The siloxane polymer of claim 1,whereinR¹ to R⁵ may be the same or different and are hydrogen atoms,linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms,mono- or poly-cyclic aryl groups having 6 to 15; R⁶ to R⁹ may be thesame or different and are hydrogen or chlorine atoms, cyano, linear,branched or cyclic alkyl groups having 1 to 6 carbon atoms, mono- orpoly-cyclic aryl groups having 6 to 10 carbon atoms, alkoxy groupshaving 1 to 6 carbon atoms, --SO₂ R¹², --SO₃ --R¹², --CO--R¹²,--CO--NH--R¹², --COO--R¹² or R¹² is a linear, branched or cyclic alkylgroup having 1 to 10 carbon atoms, or a mono- or poly-cyclic aryl grouphaving 6 to 15 carbon atoms; R¹⁰ and R¹¹ are hydrogen atoms, or linear,branched or cyclic alkyl groups having 1 to 4 carbon atoms; two of R⁶ toR⁸ and Y, or R¹⁰ and R¹¹ may combine to form a ring; Y is a single bond,a linear, branched or cyclic alkylene group having 1 to 4 carbon atoms,or a mono- or poly-cyclic arylene group having 6 to 10 carbon atoms; andX¹ to X³ may be the same or different and are chlorine atoms, linear,branched or cyclic alkyl groups having 1 to 10 carbon atoms, mono- orpoly-cyclic aryl groups having 6 to 15 carbon atoms, aralkyl groupshaving 7 to 15 carbon atoms, alkoxy groups having 1 to 8 carbon atoms,or aryloxy groups having 6 to 10 carbon atoms, provided that at leasttwo of X¹, X² and X³ are chlorine atoms, alkoxy groups having 1 to 8carbon atoms or aryloxy groups having 6 to 10 carbon atoms.
 3. Thesiloxane polymer of claim 1, wherein the cyclic heat addition product isrepresented by the formula (VI), (VII), (VIII), or (IX): ##STR58##wherein R¹ to R⁹, X¹ to X³, Y and A are the same as defined in claim 18.4. The siloxane polymer of claim 1, wherein the siloxane polymercontains 10 to 80 mol % of the repeating unit obtained by hydrolysis oralkoxylation followed by the condensation of the cyclic heat additionproduct.
 5. The siloxane polymer of claim 1, wherein the condensation iscarried out in the presence of one or more compound of formula (XII),(XIII), (XIV), (XV) or (XVI):

    R.sup.16 --Si--X).sub.3                                    (XII) ##STR59## wherein R.sup.16 to R.sup.22, R.sup.24 to R.sup.26, R.sup.28 and R.sup.29 may be the same or different and each represents a hydrogen atom or an alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, silyl, substituted silyl, siloxy or substituted siloxy group;

R²³, R²⁷ and R³⁰ may be the same or different and each represents asingle bond, a bivalent alkylene group, a substituted alkylene group, anarylene group or a substituted arylene group; and X represents ahydrolyzable group.
 6. The siloxane polymer of claim 5, wherein thealkyl group is a linear, branched or cyclic alkyl group having 1 to 10carbon atoms;the substituted alkyl group is a linear, branched or cyclicalkyl group having 1 to 10 carbon atoms which is substituted with atleast one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms,an aryl group or an aryloxy group; the aryl group is selected from thegroup consisting of monocyclic and bicyclic aryl groups; the substitutedaryl group is selected from the group consisting of monocyclic andbicyclic aryl groups which are substituted with at least one groupselected from among alkyl groups having 1 to 6 carbon atoms, alkoxygroups having 1 to 6 carbon atoms, halogen atoms, or nitro, phenyl,carboxy, hydroxy, amido, imido or cyano groups; the alkenyl group is avinyl group; and the substituted alkenyl group is a vinyl group which issubstituted with alkyl groups or aryl groups.
 7. The siloxane polymer ofclaim 5, wherein the alkyl group is selected from the group consistingof methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, iso-propyl,iso-butyl, tert-butyl, 2-ethylhexyl and cyclohexyl groups;thesubstituted alkyl group is selected from the group consisting ofmonochloromethyl, dichloromethyl, trichloromethyl, bromomethyl,2-chloroethyl, 2-bromoethyl, 2-methoxyethyl, 2-ethoxyethyl,phenylmethyl, naphthylmethyl and phenoxymethyl groups; the aryl group isselected from the group consisting of phenyl, α-naphthyl and β-naphthylgroups; the substituted aryl group is selected from the group consistingof 4-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-nitrophenyl,4-hydroxyphenyl, 4-phenylphenyl, 4-methylphenyl, 2-methylphenyl,4-ethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl,2-carboxyphenyl, 4-cyanophenyl, 4-methyl-1-naphtyl, 4-chloro-1-naphthyl,5-nitro-1-naphthyl, 5-hydroxy-1-naphthyl, 6-chloro-2-naphthyl,4-bromo-2-naphthyl and 5-hydroxy-2-naphthyl groups; and the substitutedalkenyl group is selected from the group consisting of 1-methylvinyl,2-methylvinyl, 1,2-dimethylvinyl, 2-phenylvinyl,2-(p-methylphenyl)vinyl, 2-(p-methoxyphenyl)vinyl,2-(p-chlorophenyl)vinyl and 2-(o-chlorophenyl)vinyl.
 8. The siloxanepolymer of claim 1, wherein the repeating unit of the siloxane polymeris selected from the group consisting of compounds (g)-(1) to (g)-(48):##STR60## wherein D is hydrogen atom, n is an integer not less than 1and x, y and z are each an integer not less than 0.